International Journal of Hydrogen Energy 25 (2000) 425±430

The application of Mg-based metal-hydrides as heat energy

storage systems
A. Reiser*, B. BogdanovicÂ, K. Schlichte
Max-Planck-Institute fuÈr Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, MuÈlheim an der Ruhr, Germany

Abstract

Mg-based metal hydride systems are potential high temperature heat storage media. In this paper the features and
possibilities of the systems Mg/MgH2, Mg±Ni/Mg2NiH4, Mg±Fe/Mg2FeH6 and Mg±Co±H are discussed. All the
materials show cyclic stability in certain temperature ranges. The thermal energy which is released by these systems
covers a temperature range from 2508C to 5508C in which high thermal energy densities of up to 2257 kJ/kg are
reached. # 2000 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights
reserved.

1. Introduction . Mg±Fe/Mg2FeH6, Mg/MgH2 iron (Fe)-doped;

Because fossil energy-sources are limited and are as-
sociated with environmental problems, considerable
e€ort has been made to ®nd clean and cheap alterna-
tives. The use of thermal solar energy based power
stations is one possibility whereby independence from
the changing input of the sun is essential. Magnesium
hydrogen systems can act as a thermal energy storage
system [1±6], this has been demonstrated in a test facil-
ity of 10 kWh storage capacity [1,4]. Particularly ad-
vantageous is the ability of such systems to deliver
heat energy at a constant temperature which can be
controlled by the applied H2-pressure. In this connec-
tion the relative good heat conduction of Mg/MgH2
[4,7] is of signi®cance. To show the wide operation
®eld of the di€erent Mg-based hydrides, the systems:
. Mg/MgH2, Nickel (Ni)-doped;
. Mg/MgH2;
. Mg±Ni/Mg2NiH4;
* Corresponding author.
. Mg±Co/Mg2CoH5/Mg6Co2H11
are presented and compared in this paper. Features
such as the energy density, thermodynamic properties,
temperature operating range, cyclic stability and prep-
aration will be discussed in turn for each Mg-based
system.
2. The di€erent Mg-based systems
2.1. The pure Mg/MgH2 system
The pure Mg/MgH2 system has the highest usable
H2-content, but due to its thermodynamic stability
(72±75 kJ/mol H2) [8] it is not particularly suitable for
hydrogen storage. However, if the reaction of Mg and
hydrogen is used to store thermal energy a theoretical
energy density of 2814 kJ/kg is possible. In order to
obtain a full conversion to MgH2, Mg-particles of 25±
100 mm size are needed and to obtain a reasonable
speed of reaction, a minimum temperature of at least

0360-3199/00/$20.00 # 2000 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.
PII: S 0 3 6 0 - 3 1 9 9 ( 9 9 ) 0 0 0 5 7 - 9
426 A. Reiser et al. / International Journal of Hydrogen Energy 25 (2000) 425±430
Fig. 1. SEM-picture of the starting Mg-powder, enlargement
factor: 500 [9].
3508C is necessary. A critical factor is the applied tem-
perature during the hydrogenation and dehydrogena-
tion cycle: undoped Mg needs a minimum
decomposition-temperature of 3208C under normal
pressure. If, however, the decomposition temperature
is raised to about 4508C, the Mg metal begins to
agglomerate and as a result the particles do not com-
pletely react with hydrogen. The appearance of the
starting material is shown in Fig. 1 while that of the
Fig. 2. SEM-picture of agglomerated Mg-particles, enlarge-
ment factor: 100 [9].
same material after 700 cycles between 475±5228C and
115±130 bar is shown in Fig. 2: the single particles
have agglomerated and fused together [9].
This disadvantage, which becomes magni®ed upon
raising the temperature, is associated with the high
vapour pressure (0.133 bar at 5008C) of Mg-metal and
the relatively low melting point (Tm=6508C). Hence, it
is important to reduce the time during which the ma-
terial is kept in a desorbed state as Mg-metal, in order
to minimize the loss of capacity above 4508C. Despite
this limitation many studies show the cyclic stability of
Mg/MgH2 [10,11]; see also [12,13].
2.2. The Ni-doped Mg/MgH2 system
The easiest way to prepare Ni-doped systems is to
mix the two metal powders. A more sophisticated wet-
chemical method has been developed which leads to a
very ®ne dispersion of Ni-particles on the surface of
the Mg [14]. To achieve the same catalytic e€ect with
the powder-method 5 wt% Ni are necessary compared
to 2 wt% using the chemical method. In the presence
of the catalyst the hydrogenation reaction starts at
2308C. Fig. 3 shows the result for the mildest con-
ditions using the chemical doped material, it should be
noted that the high hydrogen content of 6 wt% is
attained.
However, for both systems high temperatures must
be avoided since the eutectic melting point between
Mg and Ni is 5068C. In practice temperatures over
4208C should be avoided [15]. The cyclic stability of
this system has been demonstrated in several tests, one
of which exceeded 10,000 cycles [16]. Assuming a
hydrogen content of 6 wt%, the observed energy den-
sity of 2147 kJ/kg approaches the theoretical value of
2741 kJ/kg.
Fig. 3. Cyclic stability of chemical Ni-doped Mg. Conditions:
230±3708C and 4.0±1.4 bar, time for one full cycle 3 h.
 A. Reiser et al. / International Journal of Hydrogen Energy 25 (2000) 425±430
Fig. 4. Cyclic stability of Mg2Ni. Conditions: 230±3308C and
0.4±2.8 bar, time for one full cycle 3 h.
2.3. The Mg±Ni/Mg2NiH4 system
Mg2Ni powder can be prepared by melting and
crushing. The advantage of this material Ð the very
fast hydrogenation reaction at very low temperatures
Ð is, however, associated with a reduction in capacity
(theoretical 3.6 wt%). Mg2NiH4 is less stable than
MgH2 and has an enthalpy of formation of 62±64 kJ/
mol [17,18]. The lowest hydrogenation temperature
which we have observed is 2308C using an excess press-
ure of 0.4±4 bar. The full cyclic stability test is shown
in Fig. 4. With a capacity of 3 wt%, an energy density
of 916 kJ/kg is observed. Good cyclic stability has also
been observed by [19] (1380 cycles) and [20] (1500
cycles).
2.4. The Mg±Fe/Mg2FeH6 system
The interest in high temperature storage systems
having good cyclic stability has its origin in the Car-
not-cycle: the eciency of the conversion of heat to
mechanical energy increases upon raising the working
temperature. The Mg2FeH6 system has shown itself to
Fig. 5. Cyclic stability of Mg2FeH6. Conditions: 473±5528C
and 77±85 bar, time for one full cycle 3 h.
427
Fig. 6. Cyclic stability of a 2:1 mixture of Mg±Co. Con-
ditions: 420±5558C and 38±42 bar, time for one full cycle 3 h.
be particularly valuable for this task [9]. The ternary
hydride phase can be conveniently generated by using
a cyclic procedure which is completed after approxi-
mately 20 cycles (3 h) and one 24 h hydrogenation
whereby a pressure of 80±90 bar and temperatures
between 470±5508C are necessary [21]. In Fig. 5, the
excellent cyclic stability of the material at a capacity
level of about 5 wt% is shown. The system theoreti-
cally stores 5.47 wt% hydrogen and the enthalpy of
formation has been shown to be 77 kJ/kg [9].
The high stability of Mg2FeH6 requires desorption
temperatures of at least 5008C, while a satisfactory
rate of hydrogenation is observed at temperatures of at
least 4508C. Desorption-temperatures of up to 5908C
have been tested and did not a€ect the cyclic stability
of the material. Furthermore, the addition of Fe to the
Mg-powder (4:1±20:1, 480±5508C, 80±88 bar) has been
shown to signi®cantly improve the cyclic-stability com-
pared to undoped Mg. The cyclic stability of the Mg±
Fe/Mg2FeH6-system at this high temperature is the
result of the inability of the two metals to form an
alloy under these conditions. As a result the metals
separate and then reform a unique phase during
hydrogenation.
2.5. The Mg±Co±H system
The two ternary hydrides Mg2CoH5 and Mg6Co2H11
are known in the Mg±Co±H system. The method of
synthesis and the crystallographical features have been
described in detail by Yvon et al. [22±25] and in [26],
but there is disagreement concerning the thermodyn-
amic data. Yvon et al. published a value of 86 kJ/mol
H2 for the heat of dissociation and 60 kJ/mol H2 for
the heat of formation for the Mg2CoH5 phase, which
means a considerable hysteresis [23]. Similar but
slightly lower values were reported by Konstanchuk
[25] who performed a series of desorption PCI-
measurements and found two hydride-phases. The
428 A. Reiser et al. / International Journal of Hydrogen Energy 25 (2000) 425±430
Fig. 7. PCI-diagram of a 2:1 mixture of Mg±Co.
lower pressure plateau corresponding to a heat of for-
mation of 70 kJ/mol H2 and the higher one to 79 kJ/
mol. Additional desorption measurements by Yvon et
al. with a thermobalance yields desorption values of
95 kJ/mol H2 and 108 kJ/mol H2 respectively [26]. The
theoretical hydrogen capacities of Mg2CoH5 (4.48
wt%) and Mg6Co2H11 (4.04 wt%) are relatively small
compared to the binary counterpart MgH2 (7.66 wt%),
which would be more ecient as a hydrogen storage
material. But despite the deviations for the thermodyn-
amic data the stability of the material is high enough
to act as a heat energy storage system. Therefore an
extended cyclic-stability test was carried out with a
mixture of Mg and Co-powder in a ratio of 2:1 (Fig.
6). The result shows clearly the excellent cyclic stability
of this material over more than 1000 cycles. We
assume that under these conditions the Mg6Co2H11
hydride phase is partly formed. After the material had
been subjected to the long term cyclic test additional
desorption PCI-measurements at 440, 468 and 4868C
were performed (Fig. 7). In the range of a hydrogen
content up to about 2.5 wt% a plateau was found.
The equilibrium pressures in this region correspond to
a heat of desorption of about 76 kJ/mol H2 2 4 kJ/
mol. From there up to about 3.7 wt% a second vari-
able plateau exists in this region no reliable value for
the heat of formation could be calculated. Nevertheless
it is shown that the Mg±Co±H system possesses a su-
Table 1
Di€erent temperature ranges of the thermal output
Material Usable temperature range (8C)
Mg±Ni/Mg2NiH4 250±350
Mg/MgH2+2 wt% Ni 290±420
Mg/MgH2 350±450
Mg/MgH2+10 wt% Fe 350±550
Mg±Fe/Mg2FeH6 450±550
Mg±Co/Mg2CoH5 450±550a
a
Preliminary results.
Fig. 8. Dissociation-pressure-diagram for the MgH2,
Mg2NiH4, Mg2FeH6 and Mg±Co±H system.
ciently high enthalpy of formation to be regarded as a
heat storage media. In addition the dissociation press-
ure of the ®rst plateau is much lower than that of the
other systems discussed above. This is of considerable
importance for a more simple design of the pressure
vessels which store the hydride under H2-pressure and
a high temperature (>5008C). Further investigations
with di€erent Mg and Co ratios are necessary to
obtain reliable data of the thermodynamic stability of
both hydride phases.
3. Comparison of the di€erent Mg-based metal hydride
systems
The most important di€erence in the ®ve systems is
the temperature at which they can produce thermal
energy. The usable temperature for the systems with
Mg±Ni/Mg2NiH4, Mg/MgH2+2 wt% Ni, Mg/MgH2,
Mg±Fe/Mg2FeH6 and Mg±Co±H increases from 250
to 5508C (Table 1).
In most cases the temperature range will dominate
the choice of material. But the maximum practical
possible energy density is also an interesting feature.
The following calculations are based on the hydride
phase and the parameters used are found during our
experiments. In addition, it must be emphasized that it
is dicult to determine exactly enthalpy data (for
example Mg±MgH2 72±75 kJ/mol) and as a result de-
viations of more than 1000 kJ/kg in the value of the
energy density are possible. In Table 2 the di€erent
materials are listed according to their thermodynamic
properties along with the theoretical and practical
energy densities. The system Mg±Ni/Mg2NiH4 yields
the smallest value due to the low enthalpy of for-
mation and the high weight of the metals. In contrast
the Ni doped Mg system has a value twice as large.
In addition to the practical energy densities, the
 A. Reiser et al. / International Journal of Hydrogen Energy 25 (2000) 425±430 429

kJ/dm3
kJ/dm3
kJ/mol
Table 3

g/cm3
g/cm3

kJ/kg
kJ/kg
wt%
wt%
Coecients for the desorption pressure function

System a b

Mg±Co/Mg2CoH5
Mg/MgH2 ÿ8984.4 ÿ16.2
Mg±Ni/Mg2NiH4 ÿ7439.8 ÿ14.3
Mg±Fe/Mg2FeH6 ÿ9526.9 ÿ16.5

4.48
2.7a
1.1a
Mg±Co/Mg2CoH5a

3.5
ÿ8666.5 ÿ14.4

4353
1612
76a

1260a

1386a
Mg±Co/Mg6CoH11a ÿ10060.5 ÿ17.4

a
Not ensured values.
Mg±Co/Mg6CoH11

equilibrium pressure must be taken into account if

pressure vessels are designed. In general the function
for the dissociation pressure is given as:
4.04
2.7a
1.1a

3.5

4389
1602
89a

1472a

1527a
ln P‰barŠ ˆ a=T ÿ b

The coecients a and b are listed for the di€erent sys-

tems in Table 3. The resulting dissociating pressures
Mg±Fe/Mg2FeH6

are shown in Fig. 8.

2.74
1.22
5.47
77.2

5447
1988
1817

2217
5

4. Conclusion

The energy-density (up to 2257 kJ/kg) of the dis-

Mg/MgH2

cussed metal hydride systems is much higher than that

1.42

7.66

of comparable latent heat storage systems [27]. This, as

0.8

3995
2814
1837

1469
74

well as the favourable dynamic behaviour, make them

attractive for technical application. For a fast and
economic implementation low dissociation pressures
Mg/MgH2+2 wt% Ni

are necessary and therefore the systems Mg±Fe and

Mg±Co are of special interest and warrant further in-
vestigation.
Data used for calculating the theoretical and practical energy densities

1.42

7.48
0.8

3995
2814
2257

1806
74

Acknowledgements

The authors thank Professor P. W. Jolly for useful

MgNi/Mg2NiH4

discussions and the Fonds der Chemischen Industrie

for the ®nancial support.
2.74a

3.66
62.2

0.9

3061
1117
916

824
3

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Theo.
Theo.

Theo.
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Prac.

Prac.

Prac.

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