-

IE
Volume29 Number3
March 1990
Pages 223-328

International Edition in English

Active MgH,-Mg Systems for Reversible Chemical Energy Storage

By Borislav Bogdanovii.,” Alfred Ritter, and Bernd Spliethoff
Dedicated to Professor Gunther Wilke on the occasion of his 65th birthday

An overview of the importance of and methods available for heat storage in the form of
sensible and latent heat is followed by a discussion of the advantages and disadvantages of
reversible thermochemical energy storage compared to conventional energy sources such as
fuels, i.e. irreversible chemical energy carriers. Of the reversible metal-hydride-metal systems,
the MgH,-Mg system is particularly attractive as a hydrogen and a high-temperature heat
storage material because of its high hydrogen content and the high energy content of the
Mg-H bond. The advances made in this area over the past few years, namely in catalytic
hydrogenation and the doping of magnesium powders, have led to the development of “active
MgH,-Mg systems” for energy storage. The first experimental results on high-temperature
heat storage (also with cooling) by coupling a MgH,-Mg storage system with a low-temper-
ature metal hydride storage system are presented.

1. Introduction
For thousands of years--ever since the discovery of fire-
mankind has conveniently satisfied its energy needs by burn-
ing wood or fossil fuels, thus liberating, in the form of high
grade heat, solar energy which had been stored chemically
for years (or millions of years) by photosynthesis. The energy
problem currently facing us primarily arises from an incorri-
gible disparity between the storage of solar energy in nature
and our energy consumption, which will lead, on the one
hand, to a serious shortage of fossil fuels and, on the other,
most probably to a climatic change through a build-up of
carbon dioxide in the atmosphere (“greenhouse-effect”).
This problem may be resolved, however, by: 1) reduction of
[*I Prof. Dr. B. Bogdanovii, DipLIng. B. Spliethoff
Max-Planck-Institut fur Kohlenforschung
Kaiser-Wilhelm-Platz 1, D-4330 Mulheim an der Ruhr 1 (FRG)
Dr. A. Ritter
Max-Planck-Institut fur Strahlenchemie
Stiftstrasse 34-36, D-4330 Mulheim an der Ruhr 1 (FRG)
the use of fossil fuels in favor of other energy sources, such
as nuclear power, water power and wind power; 2) intelli-
gent, more economical energy consumption;“] 3) the search
for, and use of energy storage systems which obtain their
energy from a primary energy source, e.g. from the sun, and
whose energy transformations occur in a closed cycle and
hence are environmentally unobjectionable.[’’ The following
review article describes, inter alia, an experimental chemical
contribution to the last of these three possibilities.
2. The Importance of Energy and Heat Storage,
especially of High-Temperature Heat Storage r31
The necessity of energy storage in general, and of heat
storage in particular, arises from the fact that there is a
temporal and intensity mismatch and also a spatial separa-
tion between the energy supply from an available energy
source and our need or consumption of energy. Energy stor-
age can offset this incongruity, improve the efficiency of an

Angew Chem. / n l . Ed. Engl. 29 (1990) 223-234 8 VCH Verlugsgesellschaj’i mbH. 0.6940 Weinheim, 1990 0570-0833/90j0303-0223 $02.50/0 223
energy supply system and hence reduce the energy costs.
Consequently, energy storage is a major factor in energy
saving and conservation. The storage of energy from a peri-
odic or intermittent energy source, such as the sun, is of
prime importance.
The type and magnitude of the mismatch between energy
supply and need are exemplified in Figure 1.[41 Figure 1 (a)
shows the case of constant energy supply with, however, a
brief peak load which must be covered by energy storage. In
case (b), the energy supply is periodic (solar energy), while
the energy requirement remains constant; a significant part
of the energy must, therefore, be stored during daytime in
order to cover the needs at any time. Finally, when energy
supply and demand are out of phase, as in (c), the total
energy requirement must be stored (e.g., nocturnal indoor
heating via solar heat).
The potential significance of heat storage, is impressively
demonstrated by the fact that sufficient solar energy could be
collected on the roof of a building during the summer for
covering the heating requirements of the building during the
winter (Fig. 2). In the case of a typical one-family house in
Germany with a roof surface of 100 m2-either facing south
or oriented horizontally (flat roof)-an average incident so-
lar radiation of lo5 kWhC5]could be collected per year. This
energy is sufficient to produce an amount of warm water
equivalent to that requiring approximately 10 000 L of heat-
ing oil, i.e., an amount which is more than adequate for
heating a household during the winter. If one could make use
of this energy in all of the households in the FRG, then up
to ca. 40% of the currently consumed primary energy could
be saved.
The amount of warm water whose energy content on
cooling from, e.g., 90” to 40°C corresponds to that of
10000 L of heating oil has however, in the ideal case, i.e.
without heat storage loss, a volume of 1724 m3. This is far
larger than the volume of an average one-family house. Be-
cause of the unavoidable heat losses which constantly occur
due to insulation problems, the volume of the warm-water
storage tank would have to be substantially larger. Thus, it
is immediately apparent that the, as yet, unsolved problem of
seasonal heat storage is the main reason why solar radiation
can presently play only an insignificant role as a source
of energy, particularly in more northerly latitude^.[^.^]
An important aspect in connection with the amount of
stored heat, namely the quality of the energy, or the so-called
“exergy”, should not be overlooked. Heat energy can be
converted into other forms of energy with good Carnot effi-
ciency, e.g. mechanical or electrical energy, but only above

Borislav BogdanoviC was born in 1934 in Navi Sad, Yugoslavia and studied chemistry at the
University of Belgrade. He gained his doctorate in 1962 under the supervision of G. Wilke at the
Technische Hochschule Aachen. Since 1960 he has been working at the Max-Planck-lnstitut fur
Kohlenforschung in Miilheim an der Ruhr, where he is now head of a catalysis department.
BogdanoviC habilitated in 1974 at the Universitat Bochum where he was awarded a professorship
in 1976. His research interests center on organometallic chemistry and catalysis and its applica-
tions in organic and inorganic synthesis; in 1986 he was awarded the Ruhrpreis fur Kunst und
Wissenschaft der Stadt Miilheim an der Ruhr for his more recent works on the storage of energy
with the MgH,-Mg system.

Alfred Ritter was born in 1928 in Rottweil am Neckar and studied chemistry at the Technische
Hochschule Stuttgart (where he gained his doctorate under L. Birkofer). Thereafter he worked
as a scientific assistant at the Universitat Koln and was engaged in research on organosilicon
reactions in organic synthesis. In 1963 he was awarded a fellowship grant by the Dow Corning
Corporation (Midland, Michigan) for research with L. H. Sommer at the Pennsylvania State
University. Since 1964 he has been in charge of a research group at the Max-Planck-lnstitut fGr
Strahlenchemie in Miilheim an der Ruhr. His current interests center on the radiation chemistry
of organosilicon compounds and reversible chemical reactions for the storage of solar energy.

Bernd Spliethoff was born in 1953 in Oberhausen and completed his training as a laboratory
technician at the Max-Planck-lnstitut fur Kohlenforschung in Miilheim an der Ruhr. In 1971 he
won the Bundeskanzler’s Prize f o r young scientists in the open competition “Jugend forscht ”.
Since completing his studies in engineering science at the Gesamthochschule Essen in 1975 he has
been working at the Max-Planck-lnstitut fur Kohlenforschung. He has participated right from
the beginning in the development ofactive MgH,-Mg systems as energy storers; he has developed
measuring instruments and measuring techniquesfor the characterization oftheir storage proper-
ties.

224 Angew. Chem I n ! . Ed. Engl 29 (1990) 223-234

 3. Methods of Heat Storage
a’ I
The oldest and simplest method used in everday life, as in
industry, is to store heat in the form of sensible (perceptible)
heat using materials having a high specific heat c. The mate-
L t-
rials most commonly used, and their heat capacities, are
listed in Table 1.

Table 1. Frequently used liquid and solid materials for the storage of sensible
heat [3 a, b] .

M.p. Temperature e <

range
[“CI [“Cl [gicm’] [kJ kg-’ K - ’ I
Water 0 0-100 0.98 [a] 4-19
Thermo-oils - 70/ - 10 UP to 350 [b] 0.87 [a] 2.1
18= 53KN0,/40NaN02/ 142 up to 450 1.85 [a] 1.3
t- 7NaN0, [c]
Na 98 - - 0.84 1 26
Cast iron 1150-1300 - - 7.2 [d] 0.54
Aluminum 660 - - 2.7 [d] 0.92
Fire-clay - - - 2.1 -2.6 [d] 1 .0
AI,O, 1700 - - 3.0 [d] 10
MgO 1700 - _ 3.0 [d] 1 .o
Stone - - - 1.9-2.6 [d] 0 8-0.9
Concrete - _ - 0.9

[a] Average density in the temperature range Dven. [b] Some thermo-oils can be
used up to 390°C. [c] Wt.%. [dl At room temperature.

6- 18W 6-
t-
Fig. 1. Energy available from store a,which balances out the mismatch be- A further basic method for reversible heat storage consists
tween energy supply (. - .) and need (-): a) constant energy supply, short peak in storing the heat evolved in a solid-liquid phase transition
period: b) constant energy requirement, variable (periodic) energy supply dur-
ing a half-day cycle; c) phase shift between energy supply and need; the entire
process in the form of latent heat. The advantage over the
energy need is covered by stored energy [3a] (reproduced by kind permission of storage of sensible heat is the higher energy density and that
Kluwer Academic Publishers). the temperature remains constant during the heat storage
and heat recovery processes. In contrast to the systems for
the storage of sensible heat, those for the storage of latent
300-400 “C. Consequently, energy storage systems must be heat are still at an early stage of development. A list of
developed, not only for low-temperature heat (LT) but also possible materials for this purpose is given in Table 2.
for high-temperature heat (HT).
An example of the spatial separation between energy
supply and need, is provided by electrical power plants, Table 2. Data for several potential latent heat stores [3a, b].
which produce large amounts of low-grade waste heat, but
M.p. Heat of fusion
owing to the distances between supply and consumer, often [“CI [kJ kg-’1
only part of this heat can be economically used for domestic
Salt hydrates 0- 150 100-300
heating (“power-heat-coupling”). Parafins 20-65 150- 200
LiOH 471 1080
LiF 848 1050
48 NaCI/52 MgCI, [a] 450 43 1
67LiF/33MgF2 [a] 741 900
67NaF/33MgF2 [a] 832 618
1 24.5NaC1/20.5 KClj55 MgCl, [a] 385-393 410
/
,
/ [a] Wt.%.
/

The demand for high energy content per unit weight and
volume especially in the case of mobile energy carriers,I71as
well as high exergetic quality and constant temperature, to-
gether with an unlimited storability of the stored energy,
usually can only be satisfied by chemically stored energy, i.e.,
J F M A M J J A S O N D by fuels and not by sensible heat. An advantage of chemical-
t- ly stored energy is its direct transformability not only into
Fig. 2. Utilizable solar energy and heating energy needs in summer and winter. heat, but also into other forms of energy with high efficiency
-rooftop solar energy, - - - heating energy need. (e.g., into electrical energy via fuel cells). The basic proce-

Angeu. Chem. Int. Ed. Engl. 29 (1990) 223-234 225

dures for transforming heat energy into chemical energy are
dealt with in the following section.
4. Energy Storage from the Chemist's Viewpoint;
Reversible and Irreversible Chemical Energy
and Heat Storage
A list of the best-known fuels and their energy densities is
given in Table 3. In general, the energy densities of the con-
ventional energy carriers are much higher than those of the
potential reversible chemical energy storage systems
(Table 4). One should, however, take into consideration that
these high energy densities arise from the fact that the com-
bustion process generally occurs in an open system in the
presence of oxygen from the environment, and this oxygen is
not taken into account in the energy density calculation.['l If
the combustion were to take place in a closed system and if
the amount of the consumed oxygen were to be considered in
the calculation of the energy density, then, e.g., in the case of
hydrogen as a rocket propellant the energy density would
drop to 14 x l o 3 kJkg- and in the case of gasoline to
10 x lo3 kJkg-'.
Table 3. Most common fuels and their energy densities.
Fuel Energy density
[kJ kg-'1
Hydrogen 125 103
Methane 48 103
Petrol 44.5 x 103
Heating oil 39.6 103
Cod1 29.9 x 103
Wood 15.1 103
Ethanol 28.8 103
Methanol 21.6 x 103
A major disadvantage, both in the case of conventional
energy sources and of hydrogenlgl (Table 3) is the practical
irreversibility of the combustion reaction. The combustion
processes occur a t temperatures much lower than those at
which the combustion products CO, and H,O are in thermo-
dynamic equilibrium with fuels and oxygen. This means that
the regeneration of the combustion products CO, and/or
water in fuels and 0, by direct thermochemical pathways is
not feasible because of the extremely high temperatures
which would be required. The indirect thermochemical" O1
procedures for achieving this for water are presently being
intensively investigated, while the photochemical meth-
ods" 'I are still a t an early stage of development.
In the following, we will concentrate on the problems of
heat storage. Its importance becomes immediately apparent
through the fact that, apart from the fossil energy sources,
the major remaining primary energy sources-nuclear ener-
gy and solar energy-Aeliver their energy in the form of
high-quality heat o r in the form of electromagnetic radiation
which can immediately be converted into high-quality heat.
Independent of the fact, whether nuclear or solar energy is
the primary energy source, it is necessary to search for new,
reversible (i.e., closed), ecologically compatible cycles for
226
heat storage. These should preferentially be reversible chem-
ical systems, as mentioned in the previous section. This poses
the question: How can heat be reversibly transformed into
chemical energy?
In the reversible thermochemical ['21 storage of energy the
heat of a reversible chemical reaction is stored in the form of
chemical energy. Thus, a compound of, e.g., type A-B can,
by take up of heat (positive A H , endothermic process, heat
storage), dissociate reversibly into the components A and B
(molecules or atoms) and hence transform the heat energy
AH into the chemical energy of the system A + B [Eq. (a)],
+
If the reverse reaction of A B to A-B is prevented by
heat storage
A-B + AH 7
heat recovery
A-
+B
separating A from B, or by the absence of a catalyst in the
case of a catalytic reaction, then the amount of heat A H
stored in chemical form can be stored without any loss. On
combining A and B o r on catalysis, the reaction proceeds in
the opposite sense liberating the amount of heat A H [ 1 3 1
(exothermic process, heat recovery). If A-B and A + B are in
chemical equilibrium, then displacement of the equilibrium
in favor of A + B o r A-B will depend on the amount of heat
added to o r withdrawn from the system ("self-regulating
systems", "chemical heat buffer").
Two thermodynamically based criteria must be fulfilled by
potential chemical reactions for heat storage: for high energy
density a high heat of reaction AH is required; for technical
reasons the reaction must be reversible in a temperature re-
gion adjusted to that of the heat source. The temperatures
should not be too high (for instance, above 1000"C),because
of material and heat insulation problems.['41 As will be
shown in the following, high energy densities can generally
only be achieved in reactions which have high turning tem-
peratures T*.[l5]In other words: The reversibility of a chem-
ical reaction at an acceptably low temperature can only be
achieved by loss of energy density, i.e. compared to the case
of irreversible heat storage (fuels), compromises concerning
the energy densities must be accepted.
For a chemical reaction at equilibrium, Equation (b) holds
true.
A F = AH - TAS = 0 (b)
According to this the turning temperature is, to a first ap-
proximation,"'] given by Equation (c).
AH
T* = ~
AS
It therefore follows that the turning temperature T* does not
exceed a certain value, and high energy densities (cf. A m can
only be achieved if the reaction proceeds with large entropy
changes (As).[*,16] The highest entropy changes occur in
dissociation reactions with gaseous reaction products and
with large differences in the number of moles of starting
materials and reaction products [see, e.g., Eq. (d)].[161
Angen,. Chem. Inl. Ed. Engl. 29 (1990) 223-234
 According to Alejeld,[' the so-called heterogeneous va- - excellent heat transport to and from the reaction bed;
porization reactions (i.e. reactions of type (e)) are especially - availability of the storage material in large amounts and at
suitable for heat storage. low costs;
heat storage - no environmental or fire risks on handling the storage
A-B (solid or liquid) + AH 7A-
(solid or liquid) + B (gaseous) material and carrying out the storage reaction; low toxic-
heat recovery
(4 ity or corrosiveness of the materials used.

In these reactions the turning temperature T* is relatively
low and in addition the different aggregation states allow
simple separation of A from B. The thermodynamical and
technical advantages of heterogeneous vaporization are
counterbalanced by the disadvantage of the considerable in-
crease in volume, which lowers the volumetric energy density
of the total system (for a solution of this problem in the case
of the MgH,-Mg system, see Section 6).
The energetic and thermodynamic factors are not the sole
factors which are important for the choice of reactions for
reversible heat(energy)storage. Other criteria such as the fol-
lowing may also be important or even decisive:
- complete reversibility of the reaction over a large number
of cycles, i.e., no side reactions and hence no loss of stor-
age capacity;
- excellent kinetics of the heat storage and recovery process-
es; long stability and activity of the catalyst in the case of
catalytic reactions;
- possibility of stopping or controlling the heat producing
process by separation of the components from each other
or from the catalyst;
- minimal heat loss by thermal radiation;
- heat storage and recovery in desired temperature ranges;
- as constant and controllable as possible a temperature
during the heat recovery process;
- simple realization and low processing costs;
- no (or only minor) hysteresis effects; low temperature dif-
ferences between storage and recovery, i.e., minimal exer-
gy loss;
In view of the many criteria, it is obvious that the choice
of the reactions must involve compromises.
Some examples of the best-known types of reactions which
have been suggested for reversible thermochemical heat stor-
age or which are presently being investigated are given in
Table 4. Of the catalytic gas dissociation reactions, the disso-
ciation of SO, to SO, and 0, (Solchem process) and the
dissociation of NH, to give N, and H, have been particular-
ly well investigated or considered as reversible reactions for
the storage of solar energy. The technically mature NH,
dissociation (catalysis of forward and reverse reaction, sepa-
ration of the reactants, corrosiveness and toxicity) is consid-
ered to be less problematic than that of SO,
The thermal dissociation of NH,HSO, is a potential candi-
date for energy storage because of the high energy density
and relatively low reaction temperature. The Eva-Adam
process now being operated on a pilot-plant scale at the
nuclear research center Jiilich (West Germany) is based on
the known steam reforming of methane to CO and H, . This
process was developed for the transportation of nuclear reac-
tor heat to distant users according to the principle of the
chemical heat pipe.[' 91
Because of the necessity of complete reversibility, i.e., ab-
sence of side reactions, the organic chemical reactions that
were considered, apart from the methane reforming reaction,
included only the reversible catalytic dehydrogenations of
cyclohexane, methyl cyclohexane, and ethane to benzene,
toluene, and ethene, respectively.[201
All of the remaining reactions in Table4 belong to the
category of heterogeneous vaporization reactions. Of the

Table 4. Several potential reversible reactions for the thermochemical energy storage [3a, b].

Type of reaction ExampIes Temperature range r C ] Energy denslty [kJ kg-'1

so, * so, + 1/2 0, [a]

,218.

Catalytic or 520 - 960 1235

thermal dissociation NH,HSO, s NH, + H,O + SO, 921-421 201 1
Cal
Steam reformation of methane (Eva-Adam) CH,+ H , O e C O + 3H, 480- 1195 6053
CAI
Dehydrogenation of C , H , e C,H, + H,
C*i
ethane or cyclohexane
C,H,,SC,H, + 3H,
Dehydration Ca(OH),+CaO + H,O 512 - 402 1415
of metal hydroxides. MgC12.6H,0SMgC1, 4 H 2 0 + 2 H 2 0 - 3180
salt hydrates, H,SO,/H,OsH,SO, + H,O -
acids and zeolites zeolite/H,OSzeolite + H,O so-150 914-1370
NH,-elimination from salt ammoniates C a C I , . 8 N H , ~ C a C I 2 - 4 N H+
34NH, 32-100 145

Thermal dissociation CaCO, eCaO + CO, - 1780

of metal carbonates *
MgCO, MgO + CO, 421-321 1200
Thermal deoxygenation Na,O, s Na,O + 112 0, 650-975 1531
of metal oxides 2KO,+K,O + 1 112 0, 300 - 800 2148
BaO, s BaO + 1/2 0, 300-825 528
Thermal dehydrogenation of metal hydrides see Section 5 and Table 5

[a] Solchem process.

Angew. Chem. Inl. Ed. Engl. 29 (1990) 223-234 227

dehydration reactions, slaked lime, Ca(OH), ,has been par-
ticularly well investigated for the storage of solar heat, as
have also the salt hydrates (e.g., MgCl, . 6 H,O) and H,SO,,
in addition to the reversible adsorption of water on zeo-
lites.'" In contrast, the thermal dissociation of metal car-
bonates and the reversible thermal dissociation of several
metal oxides and peroxides ("reversible oxidation") have
hardly been investigated for heat storage purposes. Apart
from the advantage of easy separation of the gaseous reac-
tion products from the solids, positive aspects in the dehy-
dration and in the thermal dissociation of ammoniates and
carbonates include the easy condensation of water vapor,
NH, and CO,, which means that large spaces for interim gas
storage are not required. A particular advantage of "re-
versible oxidation" compared to other reversible reactions
would be the possibility of storing heat in an open system.'']
Apart from very few exceptions (Eva-Adam process," I'
the Na,S . H,O system [''I) the reactions mentioned have
thus far only been investigated on a laboratory scale. In
many cases, the suitability of the proposed reactions was
only estimated on the basis of available physicochemical
data, while chemical investigations of the systems under con-
ditions relevant for heat storage and recovery or tests during
various cycles have not been carried out. It is thus obvious
why all of the present large-scale solar thermal storage sys-
tems are based only on sensible heat.[231
5. Metal Hydrides as Reversible Chemical
Energy Stores
Numerous metal-hydride-metal systems fulfill many of
the criteria required for reversible thermochemical heat stor-
age.[',] A special feature of the reversible metal-hydride-
metal reactions compared to other heterogeneous vapor-
ization reactions (cf. Table 4) is that the hydrogen liberated
during the thermal loading is the chemical fuel having the
highest energy density (cf. Table 3), and it is considered as
the possible future clean secondary energy source.fgl
heat storage
MH, + AH 7
heat recovery
+ nj2 H,
M-
M = metal, metal alloy, intermetallic compound
Since the reversible reaction of many metals, metal alloys
and intermetallic compounds with hydrogen [Eq. (f), right to
left] is being intensively investigated, inter aha, as a method
Table 5 . Data for several energy stores used as reversible metal hydride-metal systems.
Metal hydride- H, content g H2 per
Metal system [wt-"/o\ cm3 hydride [a]
FeTiH, ,,-FeTi
LaNi,H6-LaNi,
1.8
14
0.1
0.09
Mg,NiH4-MgzNi 3.8 0.08
MgHz-Mg 76 0.1
[a] Density of the hydride calculated from X-ray structure analyses. [b] Valid for the reaction FeTiH, ,-FeTiH,
228
for the safe storage of hydrogen with a high hydrogen densi-
ty per unit weight and volume (Table 5) for the transport of
hydrogen and as a fuel for motor vehicles, fuel cells etc.JZ4,251
the metal-hydride-metal systems should be regarded as re-
versible energy stores in a double sense, namely as hydrogen
stores and as heat stores. A fundamental difference between
the use of metal hydrides as heat stores and hydrogen stores
is that, in the former case, the heat of reaction of the hydride
formation can be used as heat while retaining the hydrogen
in a closed system during many heat storage cycles, whereas
in the latter case the hydrogen is liberated from the hydride
in an open system and is burned irreversibly to give water.
The reversibly stored chemical energy in the case of the metal
hydrides used as heat storage systems is naturally smaller
than that of hydrogen as irreversible energy carrier, but it
can be up to one third of the energy of the hydrogen bound
in the hydride, as in the case of the MgH,-Mg system.
The properties of many metal-hydride-metal systems as
reversible hydrogen storage materials are well-known and
have been thoroughly tested through many hydrogen charg-
ing and discharging cycles; such systems have already been
used commercially for preparing high purity hydrogen1251
and are used technically as inherently safe hydrogen
stores.f251Their use as materials for thermochemical heat
pumps and for air conditioners, has already been tested on a
large scale but has not yet been commercialized.f26]
On the basis of the temperature T d ,at which the decompo-
sition pressure reaches values of PH22 1 bar, B ~ c h n e r [ ~ ~ " *
subdivided metal hydrides into low (50 2 Td 2 -30°C or
lower) middle (200 2 Td 2 100 "C) and high temperature hy-
drides ( Td 2 200 "C). A list of some typical metal-hydride-
metal systems used for hydrogen storage together with char-
acteristic data is given in Table 5. The low-temperature
hydrides are characterized by relatively low hydrogen con-
tents (1.3-2.0 wt%) and low heats of hydrogenation; they
thus have low energy densities as hydrogen and heat storage
materials. Liberation of hydrogen from these hydrides is
already achieved with small amounts of low-temperature
heat (environmental heat). The low-temperature hydrides
are therefore suitable, e.g., for heat pumps, air conditioners,
and refrigerators (see Section 6). Disadvantageous, however,
are the relatively high costs of the alloys. In the case of
high-temperature hydrides, hydrogen contents of 3.8
(Mg,NiH,) to 7.6 wt.-% (MgH,) are achieved. Because of
the high stability of their metal-hydrogen bonds, they have
high heats of hydrogenation. All of these hydrides have in
common a high hydrogen storage density per unit volume of
the storage material; in all cases it exceeds that in liquid
hydrogen (0.075 g/cm3 at 20 K).
H,-dissociation AH Energy density Energy density
pressure of the [k3 per mol H,] as heat store as H, store
hydride/T [kJ kg-'1 (kJ kg-'I
3.5 bar/20"C
2 bar/20 "C
28 Ibl
32
- 300
200
2200
1700
1 bar1245 "C 65 1260 4600
1 bar1284"C 75 3079 9000
Angew. Chem. Int. Ed. Engl. 29 (1990) 223-234
6. Magnesium Hydride as an Energy Store;
Generation and Possible Applications of
Active MgH,-Mg Systems as Hydrogen and
loo1 /
High-Temperature Heat Stores

Since magnesium is the lightest of the metals or metal

alloys which can be considered for hydrogen storage, MgH,
has the highest hydrogen content[*'' and hence the highest
energy density (9 MJ/kg Mg) of all the hydrides used for this
purpose. Further principle advantages of MgH, as an energy
storage material are the low costs of magnesium metal, the
wide distribution of magnesium in nature[281and its environ-
mental compatibility. Furthermore, hydrogen storage in the
form of MgH, is much safer than the conventional storage Fig. 3. Temperature dependence of the hydrogen dissociation pressure of mag-
technology using containers under pressure. nesium hydride.
The disadvantage of magnesium hydride as a hydrogen
store, is that a relatively large amount of energy
[75 kJ mol-', Eq. (g)] at a high temperature level is needed stores in which the temperature and hence the exergetic qual-
ity of the stored energy continually decreases during the heat
MgH, + 75 k J m o l - ' s Mg + H, (g) discharge process (see Section 3), in the case of the MgH,-
capacity for heat storage: 0.9 kWh (3 MJ) per kg M g Mg systems the exergetic quality remains constant because
of the horizontal plateau of the concentration-pressure
isotherm (Fig. 4) during the hydrogenation as long as the
to displace the hydrogen, but this is advantageous for the
MgH,-Mg system when used as a heat store because, in
principle, 75 kJ per mol of heat or 0.9 kWh per kg Mg can be
25
stored at a hydrogen pressure (1 to > 100 bar) dependent
temperature level between 300 and about 500°C (Table 6,

Table 6. Temperature-dependent hydrogen dissociation pressure of magne-

sium hydride p,,,.

T ["C] PHI Fa] T "Cl P H [bar1

~ [bl

280 0.9 400 19.4 5

290 1.2 410 23.9
300 1.6 420 29.2
310 2.2 o 430 35.5 lO O 1 2 3 I 5 6
320
330
2.8
3.7
440
450
43.0
51.8
c iH2) Iwt.-%l -
340 4.11 460 62.0 Fig 4 Concentration-pressure isotherm for the MgH,-Mg system (nickel-
350 6.2 470 74.0 +
doped, 270 mesh Mg powder) at 352" (m absorption. desorption) and 402 C
360 7.9 480 87.8 (* absorption, desorption)
370 10.0 490 103.7
380 12.5 500 121.9
390 15.6
hydrogen pressure above the magnesium remains constant.
[a] Own measurements. [b] Extrapolated values based on own measurements. By regulating the H,-pressure the desired temperature level
of heat generation can be maintained because each hydrogen
pressure corresponds to a precisely fixed equilibrium temper-
Fig. 3). Hence, an extremely interesting temperature range is ature (cf. Table 6). Furthermore, the steep gradient of the
made available for possible technical uses of heat storage. hydrogen pressure in the range of 300-500 "C (Fig. 3 ) makes
Heat energy at this temperature level can be efficiently trans- it suitable for heat transformations (raising heat to a higher
formed into other forms of energy, in particular into me- temperature level) and for hydrogen compression.[26d1
chanical energy (steam turbines, Stirling motors) and electri- The disadvantages of the hydride heat stores in compari-
cal energy or via thermovoltaic cells directly into electrical son to heat stores based on sensible heat, are their cost,
energy. There are no equally suitable thermochemical sys- which cannot be estimated at present (no plant of this type
tems in this temperature region. Therefore, heat stores based is in operation, as yet), and the necessity of interim storage
on sensible or latent heat (Tables 1 and 2) are currently used of the hydrogen liberated from the hydride. The heat con-
to store high-temperature heat between 300-500 "C. In com- ductivities are comparable with those of conventional heat
parison with conventional heat storage materials in the same storage systems or, in certain cases, even better. The interme-
temperature range, magnesium hydride has the advantages diate storage of the liberated hydrogen in another metal-
of an energy density which is an order of magnitude higher metal-hydride system which has different thermodynamic
(c.f., Table I), and the chemically stored heat is free from properties can be very advantageous, since the coupling of
losses for any length of time. In contrast to sensible heat two metal hydride storage systems represents a chemical heat

AngeM Chem. In1 Ed. Engl. 29 (1990) 223-234 229

pump and hence can be used for heat transformation and for
cooling (see below).[26.291
The synthesis of MgH,[301 from the elements was first
' ] since Ale-
described in 1951 by Wiberg and B a ~ e r . ' ~Ever
feZd['71first proposed the MgH,-Mg system as a possible
candidate for heat storage because of its favorable thermo-
dynamic properties, its use has been the subject of continued
discussion. A technical evaluation concluded that there were
no economic benefits over heat stores based on sensible
heat,[321mainly because of the estimated low heat conductiv-
ity of the MgH,-Mg reaction bed and inadequate reaction
kinetics. The reason for the lack of experiments in this direc-
tion is probably due to the known poor chemical reactivity
of the pure MgH,-Mg system.[331Our own experiments have
shown that the above-mentioned shortcomings do not apply
to the active MgH,-Mg systems.
Reilly and W i ~ w a Z lshowed
[ ~ ~ ~ that the intermetallic com-
pound Mg,Ni and also magnesium that is alloyed with
metallic nickel exhibit a higher hydrogenation-dehydrogena-
tion rate than pure magnesium. This finding led to numerous
experiments involving the formation of alloys of magnesium
with other metals[33,351 in order to improve the kinetics of
the hydrogen charging and discharging processes. A magne-
sium/nickel alloy with ca. 10 wt.-% Ni[35,361 has been con-
sidered as a hydrogen storage material for hydrogen-pow-
ered vehicles, but it could only be used in combination with
a low-temperature metal hydride store or an additional heat
source, since the energy content of the exhaust gases did not
suffice in order to obtain the necessary high-temperature
heat for displacing hydrogen gas from the store.r371
Our chemical research on energy storage is mainly con-
cerned with improving the kinetics of the dehydrogenation
and hydrogenation steps of the active MgH2-Mg systems.
The work began with the so-called homogeneous cataly-
synthesis of magnesium hydride.f391The superior ki-
netics of the dehydrogenation of magnesium hydride which
had been prepared by homogeneous catalysis (referred to as
MgHT from here on), and the hydrogenation of the active
magnesium (Mg*)[33.401obtained from it, prompted our in-
vestigations on their use as energy stores. Furthermore,
MgHT and Mg* found useage as reagents in organic and
inorganic syntheses because of their high rea~tivity!~']They
have also been employed for the preparation of intermetallic
compounds and their hydrides and carbides via non-metal-
lurgic routes.[42]In the following, we shall review more re-
cent developments in the area of energy storage (for earlier
work, see Ref. [33]).
The high chemical reactivity of MgHT is considered to be
due to its generation in an inert atmosphere in the form of
microcrystals (0.05 pm) with an oxide-free and high specific
surface area (70-180 m2 g- 1).[4'1 Other possible reasons for
the superior dehydrogenation-rehydrogenation kinetics of
MgHT include the defects in the crystal lattice caused by
impurities such as MgO and MgCI, and the catalytic effect
of the transition metals (Ti, Cr)r431resulting from the te-
trahydrofuran-soluble hydrogenation catalysts which re-
main in the solid. In order to test this effect, the influence of
doping MgH? with small amounts of transition metals was
studied using the transition metals in the form of soluble
organometallic complexes or compounds and assessing the
effect on the dehydrogenation-rehydrogenation. It was
230
found that both the rate and the degree of the dehydrogena-
tion-rehydrogenation could be improved considerably by
adding small amounts (0.5-3 wt.-%) of transitional metal
complexes, especially nickel complexes, to the MgH; .[441
MgH:, as an energy storage material, has the disadvan-
tages of being highly pyrophoric and of being relatively dif-
ficult to prepare. It therefore seemed obvious to use the
above-described method of catalytic doping to improve the
properties of the commercially available magnesium pow-
ders. This led to the development of various, relatively sim-
ple methods for the preparation of storage materials based
on magnesium
The doping generally consists of treating finely ground
magnesium powders (preferentially 270 mesh or finer) or
magnesium hydride with a solution of a suitable transition
metal complex, if necessary in the presence of hydrogen. In
this way, the transition metal is deposited in an extremely
finely divided form on the surface of the Mg or MgH, parti-
cles and it assumes the role of the catalyst in the hydrogena-
tion and dehydrogenation processes. The advantages of this
method are that small amounts of the deposited transition
metal already have a strong catalytic effect and that the so
doped magnesium powders become air-stable. A typical pro-
cedure consists of doping the Mg powder with a solution
of bis( 1,s-cyc1ooctadiene)nickel (cod,Ni) 1451 in toluene by
passing hydrogen into the solution at room temperature un-
der normal pressure. The nickel complex is autocatalytically
hydrogenated to cyclooctane and nickel which is deposited
in very fine distribution on the surface of the Mg particles
[Eq. (h)l.
Mg powder (excess) + cod,Ni + 4 H, - 20 "C
-2c-C8H,,
Mg(Ni) (h)
The Mg powder (270 mesh) doped with 2 wt.-% of nickel
and obtained in this way proved to be suitable as a hydrogen
and heat storage material in numerous tests and it is used at
the present time as a standard material in our experiments
described below. The standard material has the following
properties:
- reversible hydrogen contents of 6-6.5 wt.-%,
- satisfactory and complete display of the kinetics after the
first hydrogenation,
- stability over a long period, demonstrated by extended
testing in a closed system through 1800 cycles,
- very little absorption-desorption and an al-
most horizontal plateau in the concentration-pressure
isotherm (cf. Fig. 4),
- relatively good heat conductivity of the solid MgH,-Mg
storage bed during the hydrogenation and dehydrogena-
tion (Fig. 5).14']
A further improvement of the H,-storage capacity and of
the long term stability as well as the economic optimization
of the storage material production are currently being at-
tempted.[481
Our present research in the area of energy storage is fo-
cused on the use of active MgH,-Mg systems as high temper-
ature heat stores.@,291 A heat store based on MgH,, operat-
ing on the principle shown in Equation(g), consists
essentially of a pressure-proof container interconnected with
a second container for the intermediate storage of the de-
Angew. Chem. In(. Ed. Engl. 29 (1990) 223-234

Dehydrogenation Hydrogenation
TI
I
Fig. 5. Top: opened cylindrical MgH,-Mg experimental heat store with an
internal diameter of 70 mm which can be heated or cooled externally. During
the dehydrogenation, which proceeds from the outside to the inside, as does the
heat flow. the reaction was stopped, so that two cylindrical zones were present
in the store. The slightly abraded material clearly shows an outside metallic
shining ring made of magnesium, and an inner ring consisting of MgH,. The
middle of the store has a sinter metal pipe for delivering and withdrawing
hydrogen. The irregularities within the outer ring are due to the difficulties
encountered while abrading the brittle material. By measuring the dynamic
temperature curves during the hydrogenation and dehydrogenation at various
depths in the hydride bed, the “average effective total heat conductivity” of the
MgH,-Mg system during the chemicai reaction can be determined when using
an empirical formula. This is characterized by the various single conductivities
of the MgH,-Mg material combinations which are formed from the initially
pure educts MgH, or Mg, respectively, and which are separated by the reaction
zone which always moves from the outside to the inside. Bottom: From the
narrow width of the reaction zone and the temperature jump which occurs
there, it can be concluded that the chemical reaction rate must be greater than
the rate of the heat transportation. In the inverse case, the reaction zone should
be spread over the entire width of the tube filling [47].
sorbed hydrogen. A valve regulates the flow of hydrogen
between the two containers. The intermediate storage of the
desorbed hydrogen can be achieved in three ways: 1) storage
in a gas container under normal pressure; 2) storage under
the decomposition pressure of the magnesium hydride in a
pressure-proof container; 3) storage in the form of a low-
temperature metal hydride. The latter two possiblities have
been realized and tested by us on a laboratory scale.[291
The third possibility of intermediate storage of hydrogen
is based on the use of a suitable metal alloy, which on taking
up hydrogen yields a low-temperature hydride by delivering
heat to the environment. This hydride must be able to release
the chemically bound hydrogen by taking up environmental
A n g i w Chem. In!. Ed. Engl. 29 (1990) 223-234
heat to cover the reaction enthalpy. This approach is of
particular interest for the following reasons:
- The absorption of hydrogen yielding the low-temperature
metal hydride releases low-temperature heat, which con-
stitutes 30-40% of the high-temperature heat of reaction
and can be used, for example, for chemical heat pump
processes.
- The desorption of hydrogen from the low-temperature
metal hydride results in cooling, which can be used to
produce ice or for air-conditioning purposes.
- The large temperature difference, which occurs in the
combined metal hydride systems during the reverse reac-
tion of magnesium to magnesium hydride can be used
advantageously for improving the efficiency of thermody-
namic machines such as Stirling motors or thermovoltaic
cells.
- By supplying low-temperature heat, e.g., waste heat from
industrial processes, into the low-temperature part of a
combined metal hydride system, the hydrogen pressure
can be increased, hence leading to a temperature increase
in the high-temperature section (heat transformation).
- The volume of the intermediate hydrogen storage tank is
much smaller than that of either of the alternative storage
variants.
The apparatus shown in Figure6 was used in order to
study the processes mentioned. Section A (HT heat store)
fl
Circulation
, I
Thermostat
I
I
includes a thermally insulated cylindrical stainless steel con-
tainer which is filled with 1054 g of nickel-doped magnesium
powder (standard material).[441Heat was transferred via the
upper horizontal plate of this container to the magnesium
hydride bed using an electrically heated hot plate.
Section B (LT heat store) shows the commercially avail-
able[491low-temperature metal hydride container (hydrogen
storage capacity 1 m3), which contains the alloy Code 5800
(Tio.98Zro.02V,,,, Fe,.,, Cro,05Mn,.,). This is immersed in
a water or water/glycol bath which is kept at the desired
23 1
 constant temperature using a thermostat. The two contain- that the hydrogen displacement from the MgH, store was
ers are interconnected via a copper tube in order to allow complete after about 4 h, and that the resorption required
hydrogen exchange in both directions. A high precision dig- approximately 3 h at a practically constant rate. The values
ital balance serves for the gravimetric determination of the in column 4 of Table 7 apply only to the case where the heat
absorbed/desorbed hydrogen in and from the low-tempera- of hydrogen sorption in the magnesium container is vented
ture metal hydride container. to the atmosphere by thermal radiation and natural convec-
The experimental set up shown in Figure 6 was used to tion via its thermally uninsulated upper horizontal plate. A
carry out the following experiments, the results of which are remarkable increase of hydrogen sorption is recorded when
summarized in Table 7. In all of the experiments, the rate of this plate is covered with a pot containing cold water, which
heating (405 K h- ') of the magnesium hydride container after a short time starts boiling.
from room temperature to the final temperature of 425 "C Also the data in Table 7, column 5 for the heat output
during regeneration of the magnesium hydride only apply
when the high-temperature reaction heat is given off under
Table 7. Experimental results during high-temperature heat storage and re-
the conditions described above. In an experiment carried out
covery (for experimental setup see Fig. 6).
at 10 "C on the low-temperature side of the system, the heat
Temp. of Amount Max. rate Amount Heat per- Heat ca- output could be doubled by using cold water for the heat
the LT- of H, des- of H,-de- of H, formance pacity of
metal orbed from sorption resorbed by of the the MgH,
transfer.
hydride MgH, [gl [gh-'l Mg [gl MgH, con- container The used heat capacity of the magnesium hydride contain-
["CI tainer [kW] [kWh] er (Table 7, column 6), like the maximum amount of H, des-
+ 10 69 40.4 69(6.0 h) 0.26(2 5 h) 0.71
orbed and reabsorbed by Mg per hour, decreases with in-
+ 20 69.4 33.6 69(6.0 h) [a] 0.3(2.5 h) 0.71 creasing temperature of the low-temperature metal hydride
+ 30 60.6 26.0 62.6(6.0 h) 0.33(2.0 h) 0.65 container (Table 7, column 3).
+ 40 36.4 24.0 37.6(6.0 h) 0.33(1 2 h) 0.38
In order to realize the heat recovery during a reaction
[a] 60 g after 2.5 h. cycle, one must know the lowest preheating temperature in
the magnesium container at which the hydrogen resorption
begins. On the basis of two experiments, during which the
was constant. This temperature was maintained for an addi- low-temperature metal hydride container was kept at 10 and
tional 5 h. The temperature at which the liberated hydrogen 20 "C, respectively, it could be demonstrated that the magne-
was absorbed by the low-temperature alloy was varied at sium container had to be heated to 150 "C in order to initiate
10 "C intervals between 10 and 40 "C. the heat recovery process.
The amount of absorbed hydrogen in the low-temperature The most interesting application of the storage unit shown
metal alloy, i.e. the amount of hydrogen desorbed from in Figure 6 is the simultaneous production of ice with the
MgH,, was determined by weighing the relevant container low-temperature metal hydride container and of high-tem-
on a high-precision balance (columns 2 and 3 of Table 7). perature heat by resorption of hydrogen in the magnesium
During the heat recovery, the heating plate is removed so container with reformation of magnesium hydride.
that the heat can be delivered to the surroundings via the To demonstrate this double effect, the container with the
upper plate of the autoclave. The amounts of hydrogen des- low-temperature metal alloy was cooled to 0 "C and kept at
orbed from the low-temperature metal hydride (which be- this temperature level using a water/ice bath until the hydro-
come reabsorbed by Mg) are listed in column 4 of Table 7. gen transfer from the magnesium hydride container was
The plot of the experiment carried out at 20 "C (Fig. 7) shows completed. Under these conditions, 67.2 g of hydrogen gas
are taken up within 3 h at a maximum delivery rate of
46.0 g h-' by the low-temperature metal alloy, leading to
Heat storage Heal recovery formation of the corresponding metal hydride.
TI tl'WI PIH?
I" 1 'CI (bar After completion of this step, the low-temperature metal
LO Loo- LO hydride container was immersed in a water-bath at 0 "C and
the magnesium container was heated to the preheat temper-
30 300- 30 ature, as mentioned above. After 3 h, 59.0 g of the hydrogen
is resorbed by the magnesium bed and 2.5 g more after a
20 200- 20
further two hours. This corresponds to a heat capacity of
0.64 kWh for the magnesium container. The heat perfor-
mance is almost constant over a period of 2.3 h and amounts
10 100- 10
to 0.23 kW. At the end of the reaction, 1.9 kg of ice had
formed around the low-temperature metal hydride contain-
0 0- 0 er. This is equivalent to a cooling capacity of 0.18 kWh (28 %
of the high-temperature heat capacity) and a cooling perfor-
0 1 2 3 1 5 6 mance of 0.076 kW. The temperature at the hot plate of the
f lhl- magnesium container was 315 "C during this period of ice
Fig. 7. Plot of the heat storage and recovery cycle using the setup shown in production (Table 8).
Figure 6: - weight increase or decrease of the low-temperature hydride The system shown in Figure 6 can also be used as a heat
store, - . -temperature of the high-temperature heat store, - - - . -temperature
of the low-temperature heat store, - - - H,-pressure, . . . heating and cooling transformer, as can be verified by the following experiment:
curves of the high-temperature heat store with closed valve The magnesium hydride in the container is thermally decom-

232 Angew. Chem. In1 Ed Engl 29 (1990) 223-234

Table 8. Simultaneous production of ice and high-temperature heat (for exper-
imental setup, see Fig. 6).
~
Cooling capacity of the LT-metal hydride container:
0.18 kWh (28% of the high-temperature heat capacity)
Cooling performance of the LT-metal hydride container:
0.076 kW
Operation temperature of the HT-heat store during the cooling process:
315°C
Amount of ice produced at the end of the experiment:
1.9 kg
posed by heating from 20 to 349 "C within 45 min, and the
desorbed hydrogen (76 g) is absorbed in the container with
the low-temperature metal alloy, which is kept at -2O"C,
corresponding to a final hydrogen pressure in the system of
4.3 bar.
The reverse reaction is allowed to take place at 29 "C in the
low-temperature metal hydride container. The hydrogen
pressure in the system rose from the initial 4.3 bar to
24.3 bar.
The temperature in the insulated magnesium container,
from which heat can only be emitted in accord with the
degree of insulation, rapidly rises from the initial 350 "C to
373 T,and remains at this temperature for two hours. After
a further 2 h, the temperature drops to 340 "C. The result of
this experiment shows that the initial temperature increase of
49 K in the low-temperature metal hydride container Ieads
to an upgrading of high-temperature heat in the magnesium
container of 23 K, whereby the considerable hysteresis of the
low-temperature hydride has an adverse influence.
7. Summary and Outlook
The experimental results presented in Section 6 demon-
strated, for the first time, the use of a high-temperature metal
hydride based on a pure metal and not an alloy, for the
storage of high-temperature heat. Further development
work on active MgH,-Mg systems as high-temperature heat
stores is currently being carried out at the two Max-Planck-
Institutes in Miilheim an der Ruhr (FRG) in cooperation
with BOMIN-SOLAR, Lorrach (FRG) (project leader:
Dip].-Phys. J: Kleinnxkfzter) and the Institut fur Kern-
energetik und Energiesysteme (IKE) der Universitat Stutt-
gart (FRG) (project leader: Prof. Dr.-Ing. M . Groll) with
financial support of the German Federal Ministry for Re-
search and Technology, (BMFT). A major aim of this project
is to build and test the first thermochemical energy store with
about 100 kg MgH, for solar and other energy supply sys-
tems on the basis of MgH,-Mg.lSol
From a chemist's point of view, it is still an urgent and
rewarding task to develop new and inexpensive reversible
metal hydrides with high energy densities on both the high
and low temperature sides, and also to search for other re-
versible thermochemical energy storage systems.
We would like to thank Professor Dr. G . Wilkefor his gener-
ous support of the work described above. One of us, ( B . B . ) ,
would like to thank his co-workers, mentioned in the refer-
Angen. Chem. In!. Ed. Engl. 29 (1990) 223-234
ences, for their valuable contributions to this work. We are
graleful to lhe Federal Ministry for Research and Technology,
for financial support.
Received: August 21, 1989 [A 749 IE]
German version: Angew. Chem. 102 (1990) 239
Translated by Dr. W Dahlhofl, Miilheim an der Ruhr (FRG)
[l] In this context, the energy saving homes, which require only 10% of the
average heating energy, should be mentioned: H. Erhorn, 13th National
Passive Solar Conference, Cambridge, Mass. (USA), June 20-24, 1988,
Conference Proceedings, p. 3.
[2] C.-J. Winter, Phys. Bl. 45 (1989) 264, and references cited therein.
[3] a) H. P. Garg, S . C. Mullick, A. K. Bhargava, Solar Thermal Energy Stor-
age, D. Reidel, Dordrecht 1985; b) G. Beckmann, P. V. Gilli, Thermal
Energy Storage, Springer, Vienna 1984; c) M.A.K. Lodhi, I n [ . J. Hydrogen
Energy 14 (1989) 379; d) P . Kesselring, VDZ-Ber. 288 (1977) 87; e) R. E.
West, NATO AS1 Ser., Ser. E 129 (1987) 490.
[4] See [3a], p. 3.
[S] a) A Committee of the European Community publication: Allas ubrr die
Sonnenstrahlung Europas, Verlag TUV Rheinland (1984); b) Report on the
joint meeting of the Swiss Union for Solar Energy and the German Solar
Energy Society Heizen mi! SonnetPart 3.: Speicherung, Freiburg i. B 1977.
[6] The storage and transport of heat by sea water has an important influence
on the climate in our geographical latitude (Gulf Stream).
[7] For stationary use the volumetric energy density is decisive.
[8]A. Ritter in M. Becker, K.-H. Funken (Eds.): Solarchemische Technik,
Vol. 1. Grundlagen der Solarchemie. Springer, Berlin 1989, p. 157.
[9] a) M. Fischer, Chem. 1ng.-Tech. 61 (1989) 124, and referencescited therein;
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[lo] a) K.-F. Knoche, VDI-Ber. 725 (1989) 235; b) A. Aochi, 7 Tadakoro, K.
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1111 D. Behrens (Ed.): H-vdrogen Technology, Dechema Study, Frankfurt 1986.
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[12] In contrast to photochemical energy storage, which includes photosynthe-
sis; c.f., T. J. Meyer, Arc. Chem. Res. 22 (1989) 163.
[13] Reduced by the amount of heat required to heat up A and B to reaction
temperature.
[14] With this aim, chemists are trying, e.g., to obviate the high dissociation
temperature of water by dividing the reaction H,O -t H, + 1/2 0, into
several single thermochemical steps [lo].
[15] T* = AH&/AS;,,, where C , = 0. K = 1. For exact derivation of the turn-
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1161 See [3a], p. 301.
[17] G. Alefeld, WErme 8f (1975) 89; Energie 27 (1975) 180.
[18] See [3a], pp. 336-337.
1191 L. Kugeler, Nucl. Eng. and Design 34 (1975) 65, 129.
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[21] a) See [3a], chapters 4.3, 4.5 and 4.7, and references cited therein; b) E.
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[22] See [3a], p. 394.
[23] M. Geyer, H. Klaiss, R. Tamme, YDI Ber. 704 (1988) 73.
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[25] 0. Bernauer, Int. J. Hydrogen Energy 13 (1988) 181.
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1271 LiH (12.670) and AIH, (10.0%) have higher H,-contents but are not
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[281 E. G. Rochow: SiliconandSilicones. Springer, New York 1987, pp. 58--59.
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[34] J. J. Reilly. R. H. Wiswall, Inorg. Chem. 7 (1968) 2254.
233
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[37] See [24a], p. 165.
[38] Homogeneous catalytic---since the catalyst is homogeneously dissolved in
the organic solvent (tetrahydrofuran).
[39] B. BogdanoviC, S. Liao, M. Schwickardi. P. Sikorsky, B. Spliethoff.
Angew. Chem. 92 (1980) 845; Angew. Chem. Int. Ed. Engl. 19 (1980) 818;
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