i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 8 1 8 e3 8 2 4

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Tests on a metal hydride based thermal energy storage

system

B. Satya Sekhar, P. Muthukumar*, R. Saikia

Department of Mechanical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, India

article info abstract

Article history: In this paper, the performance tests on Mg þ 30% MmNi4 based thermal energy storage
Received 16 February 2011 device is presented. Experiments were carried out at different supply pressures (10e30 bar)
Received in revised form and absorption temperatures (120e150  C). The effects of hydrogen supply pressure and
17 May 2011 absorption temperature on the amount of hydrogen/heat stored and thermal energy
Accepted 18 May 2011 storage coefficient are presented. The maximum hydrogen storage capacity of 2.5wt% is
Available online 16 July 2011 reported at the operating conditions of 20 bar supply pressure and 150  C absorption
temperature. For a given absorption temperature of 150  C, the thermal energy storage
Keywords: coefficient is found to increase from 0.5 at 10 bar to 0.74 at 30 bar supply pressure. For the
Metal hydride given operating conditions of 20 bar supply pressure and 150  C absorption temperature,
Thermal energy storage the maximum amount of heat stored is about 0.714 MJ/kg and the corresponding thermal
Performance test energy storage coefficient is 0.74.
Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction C Higher energy density, as chemical reaction heats are used.

Heat storage becomes important when the heat supply and its
usage do not coincide. Heat can be stored in the form of
sensible, latent and chemically stored heat. Conventional heat
storage systems generally use Phase Change Materials (PCMs)
[1e3] and sensible heat storage materials such as cast steels,
concrete, fire bricks, etc. The PCM heat storage and sensible
heat storage (except cast steel) systems typically suffer from
low thermal conductivities and consequently have to use
bulky host structures of high thermal conductivity materials
for heat transfer enhancement. Further, for reducing the heat
loss, they need to be well insulated. Unlike, the latent and the
sensible heat storages, in chemical energy storage heat can be
stored for a longer period of time without any thermal insu-
lation. The main advantages of reversible thermo-chemical
heat storage systems over the two preceding ones can be
summarized as follows:
C Long term storage, as heat is preserved as a stable
chemical product at ambient temperature without
deterioration or loss over a longer period of time.
C Adaptability for heat transport over longer distances.
C The exergy of the stored heat is not diminished during
unloading of the stored heat, i.e., regeneration of heat
from its stored form.
C Adaptability for a variety of useful heat transformation
processes such as heat pumps, heat transformers,
refrigeration, thermal amplification, etc.
Metal hydride based energy storage systems fall under
the category of reversible chemical heat storage systems,
which can store heat in the order of 2 MJ/kg [4]. In metal
hydride based heat storage, useful heat is released when the
hydrogen is introduced into the system at certain pressure
and temperature. The rate of heat release and the

* Corresponding author. Tel.: þ91 361 2582673; fax: þ91 361 2690762.
E-mail addresses: pmkumar@iitg.ernet.in, pmuthukkumar@yahoo.com (P. Muthukumar).
0360-3199/$ e see front matter Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.05.114
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 8 1 8 e3 8 2 4 3819

Fig. 1 e Schematic of annular cylindrical reactor.

temperature can be easily controlled by varying the
hydrogen supply pressure. Whenever, the heat is available,
hydrogen is regenerated from metal hydride and stored back
in to a container.
Reiser et al. [4] investigated the heat storage capacity,
thermodynamic properties and operating temperature range
of Mg/MgH2, MgeNi/Mg2NiH4, MgeFe/Mg2FeH6 and MgeCoeH
systems. They reported higher energy density of 2257 kJ/kg
using Mg/MgH2 þ 2 wt% Ni. Kawamura et al. [5] experimen-
tally studied the heat transfer characteristics of metal
hydrides for storing thermal energy. The possibility of using
magnesium hydrides for storing heat energy in small-scale
solar thermal power station has been demonstrated by
Wierse et al. [6]. Bogdanovic et al. [7,8] reported the perfor-
mance of a combined heat storage and heat pump system
working with Mg2Ni and Ti0.98Zr0.02V0.043Fe0.07Cr0.05Mn1.5. The
system yielded the outputs of 7.4 kWh for heating at 305  C
and 1.69 kWh for cooling at 0  C. They also investigated the
performances of the system without cooling and found that
the heating output was increased to 9.08 kWh at 370  C. Later,
Bogdanovic et al. [9], reported that Mg powders could be used
as cheap material for reversible thermo-chemical heat storage
in the temperature range of 450e500  C with the heat storage
capacities of 0.6e0.7 kWh/kg of alloy. Fisher et al. [10]
analyzed the performance of a metal hydride based the
multi-tube type heat storage system.
Even though many experimental studies on metal hydride
based thermal energy storage reported in the literature [5e9],
the effects supply pressure and absorption temperature on
the performances of the system have not been reported. In
this paper, the performance tests on a metal hydride based
heat storage system are presented. The performances of the
device are investigated at different hydrogen supply pressures
and absorption temperatures.

Fig. 2 e Test setup for heat storage device.

3820 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 8 1 8 e3 8 2 4

12

10 Mg + 30%MmNi4

Hydrogen asbsorption rate (g/min)

Ta = 150 ˚C
m = 280 g
30 bar
8

25 bar

4
20 bar
15 bar

2 10 bar

0
0 2 4 6 8
Time (min)

Fig. 3 e Effect of supply pressure on hydrogen absorption rate at 150  C.

system has higher enthalpy of formation and higher hydrogen

2. Alloy selection storage capacity, due to its slow reaction kinetics and high
absorption temperature, it is not suitable for either hydrogen
The performances of the metal hydride based heat storage storage or heat storage application in the temperature range
device depend on the proper selection of alloy within the 150e250  C. After careful investigation, Mg þ 30% MmNi4 alloy
range of its operating temperatures and pressures. The is chosen for the present experiment, as it starts absorbing
desirable properties of metal hydride alloy used for heat hydrogen at 120  C and have reasonably fast reaction kinetics.
storage application are; high hydrogen storage capacity, flat
plateau, low hysteresis, fast kinetics, easy activation, and high
melting point. Alloys with high heat of formation and low 3. Experimental set up and test procedure
disassociation pressure corresponding to high temperatures
are desirable for heat storage application. Mg based alloys 3.1. Description of the test rig
have high hydrogen storage capacity and less disassociation
pressure at elevated temperature ranges, making them suit- The schematic of a cylindrical metal hydride reactor used in
able for heat storage applications. Even though pure Mg/MgH2 the present experimental study is shown in Fig. 1. The

200
20 bar
15 bar
10 bar Mg + 30%MmNi4
160 Ta = 150 ˚C
m = 280 g
Average bed temperature (˚C)

120

80

40

0
0 5 10 15 20
Time (min)

Fig. 4 e Variation of average bed temperature at 150  C.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 8 1 8 e3 8 2 4
reactor is made of seamless stainless steel (SS-316) tube of
wall thickness of 3$5 mm. Inner tube of the reactor is a sin-
tered SS-316 filter of 2-mm pore size. A perforated copper
tube (ID ¼ 16 mm and OD ¼ 18 mm) having four copper fins
of 1 mm thickness brazed on its circumference is used to
enhance the effective thermal conductivity of the hydride
bed and also to keep the hydride powder in place during the
repeated absorption and desorption processes. One end of
the reactor is welded with an assembly of two grounded
metal sheathed “K” type thermocouples (sensitivity 0.5  C
and time constant of 0.2 s) and the other end of the reactor is
flanged with a teflon seal for leak proof. The experimental
setup used for testing the performance of the heat storage
device is illustrated in Fig. 2. A specially designed high
temperature oven of operating temperature range 30e500  C
with a accuracy 1  C is used for supplying heat at
a constant temperature during the desorption of hydrogen
from the metal hydride bed.
Heat of absorption is rejected to the ambient through
a cooling coil circuit. Piezo resistive type pressure transducers
(sensitivity 0.01 bar) of range 0e100 bar are used for measuring
the hydride equilibrium pressure (P1) and the supply pressure
(P2). A coriolis mass flow meter (sensitivity 0.001 g) is used for
measuring the hydrogen flow rate and the amount of
hydrogen absorbed/desorbed. A vacuum pumping system
consists of a rotary pump and a diffusion pump is used for
creating vacuum (about 5  105 mbar) in the setup. High-
pressure (150 bar) pack less bellow valves are fitted in the
setup at specific locations for controlling and changing the
direction of the hydrogen flow. The experimental setup is
tested for high pressure leak proof using argon gas up to
100 bar and vacuum test down to 103 mbar.
3.2. Experimental procedure
3.2.1. Activation procedure
The annular gap between the tube and the filter of the reactor
is filled with 280 g of Mg þ 30% MmNi5. For activation of
Mg þ 30% MmNi5, first the reactor is heated in the oven to
a constant temperature of 300  C and then evacuated down to
103 mbar using a vacuum pump. Hydrogen is introduced at
20 bar and again the whole system is evacuated down to
103 mbar by heating the reactor up to 300  C. By maintaining
the reactor at 150  C, hydrogen at 20 bar pressure is introduced
into the reactor through a coriolis mass flow meter. During the
first cycle of operation, about 0.3 wt% of hydrogen absorption
is recorded in 20 min. Then, the reactor is heated up to 300  C
in the furnace and the hydrogen is desorbed through
a vacuum pump. During the successive absorption/desorption
cycles, a maximum storage capacity of 2.5 wt% is reached
after 10 cycles. This indicates the completion of activation
process.
3.2.2. Procedure for absorption
Valves V4, V5, V6 and V2 are closed and valves V1 and V3 are
opened. With help of a pressure regulator, supply pressure is
fixed. Thermostatic bath is set at a desired absorption
temperature and the circulation of heat transfer fluid (thermic
oil: code: 8940102 and specific heat 2000 J/kgK) is switch on at
a constant flow rate. Valve V5 is opened, and the absorption of
3821
hydrogen is started. Rate of hydrogen absorption (from cori-
olis mass flow meter), heat transfer fluid inlet (Tf1) and outlet
(Tf2) temperatures, metal hydride bed temperatures, pressures
P1 and P2 are recorded for every 3 s using a Agilent data
acquisition system. The total amount of hydrogen absorbed is
measured directly from the coriolis mass flow meter. The
absorption process is continued till there is no significant
change in the total amount of hydrogen absorbed. The
amount of heat rejected (heat stored) during the absorption
process is calculated from the difference between heat
transfer fluid inlet and outlet temperatures and the heat
transfer fluid flow rate. The same procedure is repeated for
different supply pressures range from 10 bar to 30 bar and for
different absorption temperatures in the range of
120  Ce150  C. Due to the limitation in the maximum oper-
ating temperature of heat transfer fluid, the absorption
temperature is limited to 150  C. However, the experiment
setup is designed to operate up to 450  C.
3.2.3. Procedure for desorption
During the desorption process, the reactor is taken away from
the heat transfer fluid jacket and kept inside the high
temperature oven. The valves V1, V3, V5 and V7 are closed. The
oven temperature is set at 350  C with the help of a PID
controller. After the reactor reaches the pre-set value of
temperature, desorption of hydrogen is initiated by opening
the valves V6 and V7. The amount of hydrogen desorbed from
the reactor is noted using the coriolis mass flow meter. The
desorbed hydrogen is collected in a hydrogen reservoir. The
total amount of energy consumed by the oven during
desorption of hydrogen is measured from a single-phase
digital energy meter (sensitivity 1 W).
3.3. Performance parameters
The performances of the metal hydride based heat storage
system mainly depend on the parameters such as hydrogen
storage capacity and thermal energy storage coefficient. They
are defined as follows;
3.3.1. Hydrogen storage capacity
It indicates the amount of hydrogen that can be absorbed in an
alloy during the hydriding process at a certain temperature
and pressure. Usually, hydrogen storage capacity is expressed
in percentage weight;
Weight of the H2 absorbed
Hydrogen storage capacityðwt%Þ ¼  100
Weight of the alloy
3.3.2. Thermal energy storage coefficient [TESC]
Thermal energy storage coefficient is defined as the ratio of
amount of heat released during absorption of hydrogen (Qr) to
that of amount of heat supplied during desorption of
hydrogen (Qin).
heat releasedðQr Þ
TESC ¼
heat suppliedðQin Þ
3822 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 8 1 8 e3 8 2 4

Hydrogen storage capacity (wt %) 2 20 bar

25 bar
30 bar
15 bar

10 bar Mg + 30% Mm Ni 4
1
Ta = 150 ˚C
m = 280 g

0
0 2 4 6 8 10
Time (min)

Fig. 5 e Effect of supply pressure on hydrogen storage capacity at 150  C.

4.2. Effect of supply pressure on average bed

4. Results and discussion temperature

It is observed from the literature reported by Vijay et al. [11] It is observed from Fig. 4 that during the initial period of
that the minimum absorption temperature of Mg þ 30% absorption process, the reactor temperature (average bed
MmNi5 is about 120  C. Hence, the performance of heat temperature) increases sharply from its initial value of
storage device is tested in the temperature range of 150  C to 180  C and later decreases slowly and reaches the
120e150  C with the supply pressure range of 10e30 bar. An ambient temperature at the end of the absorption process.
uncertainty analyses was carried considering the inaccuracy Initially, when hydrogen is supplied to the reactor bed, due
of the various measurements, such as temperatures, flow to rapid reaction kinetics (high absorption rate), large
rates, and power. The maximum uncertainty involved in the amount of heat is generated. Due to the poor thermal
estimation of hydrogen storage capacity and heat storage conductivity of the hydride bed, the generated amount of
coefficient are 0.6% and 1%, respectively. heat is not being transferred to the heat transfer fluid,
resulting in sharp rise in hydride bed temperature. Since,
the hydride equilibrium pressure depends on the bed
4.1. Effect of supply pressure on hydrogen absorption temperature; it also follows the same trend. As the equi-
rate librium pressure increases, the pressure difference
(between supply pressure and hydride equilibrium pres-
Fig. 3. illustrates that the hydrogen absorption rate increases sure) becomes small which results in a slowdown of the
sharply during the initial period of absorption. This is due to reaction rate. It is also seen in Fig. 4 that the rise in
existence of large pressure difference between the supply absorption temperature is higher for higher supply pres-
pressure and the hydride equilibrium pressure. Later, due to sures. This is due to increase in reaction kinetics at higher
the increase in bed temperature and also hydride equilibrium supply pressures. The combined effects of lower heat
pressure, the reaction rate decelerates suddenly. This generation (from slower absorption rates) and improved
increases the temperature difference between the hydride bed
and the heat transfer fluid, resulting in transport of heat from
the hydride bed to the heat transfer fluid. Due to the heat Table 1 e Hydrogen storage capacity at different supply
transfer from the hydride bed to the cooling fluid and fall in pressures and absorption temperatures.
reaction rate, the hydride bed temperature decreases, result- Supply Hydrogen storage capacity (wt %)
ing in absorption of hydrogen. Hence, the absorption rate pressure at different absorption temperatures.
increases gradually, reaches its peak again, then starts (bar)
150  C 140  C 130  C 120  C
decrease and becomes zero at the end of the absorption
process. The absorption process is continued until the exis- 10 1.42 1.44 1.42 1.36
tence of driving potential in the metal hydride reaction bed, i.e 15 1.88 1.92 1.9 1.83
20 2.5 2.37 2.25 1.94
the equilibrium pressure in the metal hydride reactor
25 2.5 2.39 2.26 2.01
becomes equal to the supply pressure of the hydrogen in the 30 2.5 2.42 2.26 2.04
reactor.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 8 1 8 e3 8 2 4 3823

4
30 bar
Mg + 30%MmNi4
Ta = 150 ˚C

Amount of heat stored (kJ/kg)

3 m = 280 g
25 bar

20 bar

15 bar
2
10 bar

0
0 5 10 15 20
Time (min)

Fig. 6 e Effect of supply pressure on heat storage capacity at 150  C.

heat transfer due to higher temperature difference between absorption temperature of 150  C, the hydride reaches its
the reactor and the heat fluid caused the gradual decrease maximum storage capacity of 2.5 wt% at 20 bar and beyond
of bed temperature and promotion of further hydride which the increase in the supply pressure will not contribute
formation. to the hydrogen storage capacity. Hence, for a given absorp-
tion temperature, there exists an optimum supply pressure
4.3. Effect of supply pressure on hydrogen storage and vice versa. Hydrogen storage capacities at different supply
capacity pressures and different absorption temperatures are pre-
sented in Table 1.
The effect of supply pressure on the hydrogen storage
capacity is illustrated in Fig. 5. When the supply pressure is 4.4. Effect of supply pressure on heat storage capacity
increased from 15 to 20 bar, the hydrogen storage capacity is
found to increase from 1.88 wt% to 2.5 wt%. At higher supply The heat storage capacity indicates the amount of heat that
pressures, the storage capacities are found to be more due to can be stored in the thermal energy storage system. This is
the plateau slope of the pressure-concentration-temperature directly proportional to the amount of hydrogen absorbed.
(PCT) characteristics of the hydride alloy. At a given Therefore, its variation is similar to that of the amount of

0.8
Thermal energy storage coefficient (TESC)

0.7

0.6

0.5 Ta = 150 oC
Ta = 140 oC
Ta = 130 oC
0.4 Ta = 120 oC

Mg + 30%MmNi4
0.3 m = 280 g

0.2
0 5 10 15 20 25 30 35 40
Supply pressure (bar)

Fig. 7 e Effect of supply pressure on thermal energy storage coefficient.

3824 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 8 1 8 e3 8 2 4
hydrogen absorbed. Fig. 6 shows the amount of heat that can
be stored in the heat storage system at different supply
pressures. Due to increase in hydrogen storage capacity at
higher supply pressures, the capacity of thermal energy
storage system is also found to increase with supply pressure.
With respect to Fig. 4, during the initial stage of absorption
process, the metal hydride bed reaches higher temperature at
higher supply pressures due to high rate of heat release (rapid
reaction kinetics at higher supply pressures). Hence, the peak
of the heat storage curve for 30 bar is higher than that of
25 bar. However, the area under 30 bar and 25 bar curves are
the same. For 30 bar case, hydriding reaction is completed
much before than that of the 25 bar. For the given operating
conditions 20 bar supply pressure and 150  C absorption
temperature, the maximum reported heat storage capacity is
about 0.714 MJ/kg.
4.5. Effect of supply pressure on thermal energy storage
coefficient (TESC)
Thermal energy storage coefficient (TESC) gives the amount
of energy that can be supplied back during the absorption to
that of the heat supplied during the desorption process.
Variation of thermal energy storage coefficient at different
supply pressures is shown in Fig. 7. It is observed that with
an increase in heat release temperature (absorption
temperature), the thermal energy storage coefficient at
20 bar supply pressure is found to increase from 0.57 at
120  C to 0.74 at 150  C. It should be noted that the system is
designed to work up to the operating temperature of 450  C.
Due to the limitation in the operating temperature of heat
transfer fluid, the present experimental investigation is
restricted to 150  C. It is observed that within the supply
pressure range of 10e20 bar, the effect of supply pressure on
thermal energy storage system is appreciable, but it is not so
appreciable when the supply pressure is increased beyond
20 bar.
5. Conclusions
The performance of the metal hydride based thermal energy
storage system using 280 g of Mg þ 30% MmNi5 is studied by
investigating the effects of hydrogen supply pressures and
absorption temperatures on the heat storage capacity and the
thermal energy storage coefficient. The maximum hydrogen
storage capacity of 2.5 wt% is observed at 20 bar supply
pressure and 150  C absorption temperature. For the given
operating conditions of 20 bar supply pressure and 150  C
absorption temperature, the maximum amount of heat stored
is about 0.714 MJ/kg and the corresponding value of thermal
energy storage coefficient is 0.74. Supply pressure is having
significant effect on the amount of heat stored and thermal
energy storage coefficient up to 20 bar at 150  C.
Acknowledgements
The authors express their sincere thanks to Dr. R. Vijay,
Scientist E, International Advanced Research Centre for
Powder Metallury and New Materials (ARCI), Hyderabad, for
supplying the alloy. The authors also thank the Department of
Science and Technology (DST), Government of India (Project
No: SR/FTP/ETA-33/2007 dated 16.08.07), for their financial
support.
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