Thermal Science and Engineering Progress 19 (2020) 100653

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Thermal Science and Engineering Progress

journal homepage: www.elsevier.com/locate/tsep

Influence of effective thermal conductivity on hydrogen sorption in Mg- T

LaNi4.6Al0.4 composite hydride beds for thermal energy storage
⁎
E. Anil Kumara, , Yogesh Madariab, K. Sarath Babua, S. Srinivasa Murthyc
a
Department of Mechanical Engineering, IIT Tirupati, 517506, India
b
Department of Mechanical Engineering, Malla Reddy Engineering College (A), 500100, India
c
Interdisciplinary Centre for Energy Research, Indian Institute of Science, 560012, India

A R T I C LE I N FO A B S T R A C T

Keywords:
Thermochemical energy storage
Sorption kinetics
Magnesium Lanthanum composite hydride
Effective thermal conductivity
Thermochemical energy storage using metal hydrides is well known. Appreciable quantities of heat energy
interactions involved in the hydrogenation and dehydrogenation processes of metal hydride make the metal
hydrides suitable for the storage of thermal energy. This paper discusses the synthesis, Pressure Concentration
Isotherm (PCI) characterization and estimation of thermal properties of Mg + 50 wt% LaNi4.6Al0.4 composite
hydride suitable for thermal energy storage. Maximum theoretical energy density of 918 kJ/kg can be achieved
in the temperature range of 150–200 °C. Low values (0.1–1 W/mK) of effective thermal conductivity (ETC) of
metal hydride beds is responsible for poor heat and mass transfer characteristics of metal hydride beds. The ETC
of Mg + 50 wt% LaNi4.6Al0.4 composite hydride bed was augmented by fabricating two types of pellets. The
sorption kinetic measurements were performed for three different configurations of metal hydride beds, one with
powder composite hydride and remaining with two different types of pellets. Enhancement in ETC improved the
heat and mass transfer characteristics of the composite metal hydride bed.

1. Introduction exothermic re-absorption of hydrogen by the metal hydride bed releases

Thermal Energy Storage (TES) systems are widely used to overcome
the mismatch between energy generation and usage. Thermal energy
can be stored in different methods viz, sensible heat storage, latent heat
storage and thermochemical energy storage. Thermochemical energy
storage is having the advantage of higher energy storage density and
long term storage compared to latent and sensible heat storage tech-
nologies. The reacting materials are important for thermochemical
energy storage as they should have high-energy storage density, high
sorbent absorption capacity, low cost and thermal stability during re-
peated cycling. Solid-gas based TES systems based on ammoniated
halide salts and metal hydrides are extensively tested. Out of these two,
metal hydrides are environmentally friendly, compact and flexible for
various operating conditions.
The thermal energy storage system consists of a metal hydride bed
which desorbs hydrogen by absorbing heat from an energy source; the
released hydrogen gas is stored. When heat is required to be re-
generated, hydrogen is allowed to back in to the metal hydride bed. The
the stored heat. For the application of thermal energy storage, the metal
hydride should exhibit features like, high reversible hydrogen storage
capacity, faster kinetics, low plateau slope and suitable pressure con-
centration isotherm (PCI) characteristics. A metal hydride based heat
storage system was proposed by Takami Koseki et al. [1] to reduce the
electric power demand in daytime for building air-conditioning system.
A heat storage capacity of 13.5 MJ was obtained which is sufficient to
cool 10 m2 room for 3 h. Shafiee and McCay [2] proposed a metal
hydride based hybrid thermal energy storage system having appreciable
storage capacity and flexibility in operation but suffered slow kinetics.
A parametric study [3] performed on Mg + 30% MmNi5 based thermal
energy storage system revealed that maximum storage capacity of
714 kJ/kg is obtained at 150 °C and supply pressure of 20 bar. A
coupled metal hydride bed system of CaNi5 and LaNi5 was utilized for
laboratory scale heat storage with 3.5 kg each of the alloys [4]. The
flow rate of hydrogen was kept as 1.5 l/min. Since the operating tem-
perature range of CaNi5 (40–100 °C) is higher than that of LaNi5
(20–40 °C), CaNi5 was used for heat storage and LaNi5 was used to

Abbreviations: CMH, Composite Metal Hydride; CMHB, Composite Metal Hydride Bed; ETC, Effective Thermal Conductivity; LCMHP, Loose Composite Metal
Hydride bed; MHTES, Metal Hydride based Thermal Energy Storage; PCI, Pressure Concentration Isotherm; PCMHPGF, Pellets of Composite Metal Hydride Powder
and Graphite Flakes; PCMHPGFCu, Pellets of Composite Metal Hydride, Graphite Flakes with embedded Copper wire mesh structure; SS, Stainless Steel
⁎
Corresponding author.
E-mail address: anil@iittp.ac.in (E. Anil Kumar).

https://doi.org/10.1016/j.tsep.2020.100653
Received 15 January 2020; Received in revised form 1 July 2020; Accepted 11 July 2020
2451-9049/ © 2020 Elsevier Ltd. All rights reserved.
E. Anil Kumar, et al.
absorb the hydrogen released by CaNi5 hydride bed. When the heat
energy is required, the direction of flow of hydrogen is reversed i.e. heat
energy at lower temperature (about 40˚C) is supplied to LaNi5 hydride
bed and the consequentially released hydrogen is passed to CaNi5 bed.
To have thermal energy storage systems functioning at relatively higher
temperature ranges, the same group of researchers analysed the per-
formance of hydrides of different Zirconium based alloys.
ZrMn2−xCoxAly and ZrMn1.92−xCoxV0.08 with different proportions of
Co were tested for thermal energy storage [5]. For still higher tem-
perature range i.e. between 300 and 500 °C, Bogdanovic et al. [6]
studied the performance of Ni doped Mg. According to Reiser et al. [7],
Mg-Fe and Mg-Co systems with low dissociation pressures can be ap-
propriate for thermal energy storage systems. Very little work has been
reported to identify suitable materials to store thermal energy in the
temperature range of 150–200 °C. To bridge this gap, in this work, we
have synthesized the composite namely Mg + 50 wt% LaNi4.6Al0.4 and
tested its suitability for thermal energy storage. The performance of the
energy storage system depends on heat and mass transfer character-
istics of the metal hydride bed, which in turn depends upon Effective
Thermal Conductivity (ETC). A low value of ETC (0.1–1 W/m K) is
responsible for poor heat and mass transfer characteristics of metal
hydride beds. Numerous ways of augmenting the ETC of metal hydride
beds is reported in the literature, which are summarised in author’s
recent paper [8]. Either insertion of metallic structures of high thermal
conductivity in metal hydride beds or compacting of metal hydride
powder is commonly used technique. It is felt that a combination of
these two techniques for augmentation of ETC of metal hydride beds
can also be beneficial. Hence in the present work insertion of a metallic
structure, compacting of composite metal powder, and simultaneous
compacting and insertion of metallic structure are used to augment the
ETC of composite metal hydride bed and to study its effect on hydrogen
absorption and desorption rates of metal hydride bed.
2. Selection of thermal storage materials
Literature on metal hydride based thermal energy storage (MHTES)
suggests that Mg based metal alloys/composites are best suited for this
application due to inherent low physical density and high energy
density of Mg. Studies on characteristics of Mg based hydrides has re-
vealed that they exhibit slow kinetics and require high temperatures (in
the range of 400 °C) for achieving appropriate levels of hydrogen ab-
sorption/desorption [7,9].
Hydrogen sorption capacity is the main characteristic which de-
termines the applicability of a hydride for thermal energy storage be-
cause the quantity of heat stored directly depends on the quantity of
hydrogen desorbed. Many studies to reduce the hydrogen absorption
and desorption temperatures and to improve the kinetics of Mg based
materials have been reported. Addition of LaNi5 improves the kinetics
of Mg based LaNi5 intermetallic compounds. LaNi5 in the Mg-xwt%
LaNi5 decomposes into Mg2NiH4 and LaH3 upon exposure of hydrogen
and acts as a catalyst for the reaction [10]. A composite of Mg2Ni and
LaNi5 prepared by mechanical alloying has shown improved hydrogen
absorption and desorption kinetics and exhibited a storage capacity of
1.4–4 wt% in the temperature range of 30–350 °C at a hydrogen supply
pressure of 10 bar [11]. Absorption kinetics of Mg-(20 wt%) LaNi5 were
measured at 345 °C and 30 bar supply pressure. It was observed that
rate of absorption increased when compared to pure Mg due to the
catalytic effect of LaNi5. From the kinetics studies of Mg-(10 wt%)
LaNi5, it was found that initially chemisorption of hydrogen molecules
and later diffusion of hydrogen atoms into hydride are effecting the
kinetics of hydrogen absorption [12]. Three kinds of composites of Mg-
10 wt% LaNi5 were prepared by high energy ball milling at different
conditions. The particle size of three composites are in the range of
2–6 μm. Absorption kinetics of Mg- 10 wt% LaNi5 were measured at
300 °C and found that increase in absorption kinetics is due to small
particle size of three composites [13]. Sintered composites of Mg- x wt
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Thermal Science and Engineering Progress 19 (2020) 100653
% LaNi5 (x = 20–50) were prepared from Mg and LaNi5. The sintering
process was done at 700 °C and composites were made in the form of
pellets. For × = 20–40, the composites consist of phase of pure Mg,
Mg2Ni, La2Mg17, and small fraction of MgO and for × = 50, the
composite consist of no pure Mg, but Mg2Ni and La2Mg17 as the major
phases. Pressure composition isotherm (PCI) of Mg- 30 wt% LaNi5 is
experimented at 300 °C. The PCIs show two plateaus, lower one is due
to pure magnesium and upper one is due to Mg2Ni. The advantage of
sintering is that the composites can be easily activated. However the
absorption kinetics of sintered Mg- x wt% LaNi5 (x = 20–50) was not
performed [14]. Addition of LaNi5 improved the absorption kinetics of
Mg-LaNi5 composite but did not change the rate-limiting step. Yan-Biao
Pan et al. [15] used the Chou model to analyze the effect of LaNi5 on the
absorption kinetics of Mg-LaNi5 composite. The presence of Mg, Mg2Ni
and LaHx in Mg- 30 wt% LaNi5 makes it best suitable hydride for hy-
drogen storage as well as thermochemical energy storage. Increase of
temperature up to 300 °C increases kinetics of absorption of Mg-LaNi5
composite [15]. Even though the results reported on hydrogen storage
characteristics of Mg and LaNi5 based composites [1,11–16] showed
significant deviation from one another, these composites are still found
promising for storing hydrogen in the temperature range of 125–300 °C.
3. Material preparation and characterization
With the above background, a composite of Mg and LaNi4.6Al0.4 was
prepared using high energy ball milling. This composite starts hydrogen
absorption at a low temperature of around 125 °C and provides better
hydrogen absorption/desorption kinetics compared to pure Mg.
Blended powders of magnesium (purity 99.8%, average particle size of
300 µm) and LaNi4.6Al0.4 (average particle size of 80 µm) in equal
proportions were subjected to planetary ball milling under wet milling
conditions (toluene). Fig. 1 shows the XRD pattern for Mg, LaNi4.6Al0.4
and Mg + 50 wt% LaNi4.6Al0.4. The XRD pattern for the composite
Mg + 50 wt% LaNi4.6Al0.4 showed Mg and LaNi4.6Al0.4 peaks. It con-
firms that no formation of intermediate phases took place. The XRD
pattern indicated induced strain due to milling.
The PCIs of synthesized composite powder was measured using a
Sieverts type experimental setup, developed in–house. The setup was
fabricated using high-pressure pipe fittings, valves and sample cylin-
ders. Hydrogen gas flow was regulated manually. Hydrogen is ab-
sorbed/desorbed to or from the composite metal hydride powder in
steps from a known volume. The amount of hydrogen absorbed and
desorbed was calculated based on the mass balance of hydrogen. The
Fig. 1. XRD patterns for Mg, LaNi4.6Al0.4 and Mg + 50 wt% LaNi4.6Al0.4.
E. Anil Kumar, et al.
Fig. 2. Reactor used for PCI characterization of composites: (a) Schematic diagram, (b) Photograph of reactor.
details of experimental setup, procedure and data reduction are given
elsewhere [17]. A high-pressure high temperature reactor was fabri-
cated using SS 316 to accommodate 10 g of sample for PCI measure-
ments. Fig. 2a and b show the schematic and photographic view of the
reactor respectively.
For measurement of quantity of hydrogen absorbed/desorbed by the
composite, 10 g sample of Mg + 50 wt% LaNi4.6Al0.4 was taken in the
reactor and experiments were conducted at four different temperatures
of 125 °C, 150 °C, 175 °C and 200 °C and pressure concentration iso-
therms were obtained. Fig. 3 shows the PCI characterisation for these
conditions. With the increase in temperature, both the maximum and
recoverable absorption capacity increased significantly. The composite
absorbed more than 4 wt% hydrogen at 200 °C. As expected plateau
pressure increased with increase in temperature. It is increased from
sub-atmospheric pressure at 125 °C to above atmospheric pressure at
175 °C. A step is observed in the plateau region of PCI curves. This is
due to the presence of separate Mg and LaNi4.6Al0.4 phases in the
composite as observed in the XRD pattern. Fig. 4 shows the van’t Hoff
plot constructed using measured PCIs. The enthalpy of formation esti-
mated from the slop of the van’t Hoff plot for hydrogen absorption and
desorption processes are 45.7 and 45.1 kJ/g of H2 respectively. Using
measured reversible hydrogen capacity and enthalpy of formation the
maximum average energy storage density in the temperature range of
150–200 °C is estimated to be 918 kJ/kg.
4. Estimation of Effective thermal conductivity of powder and
pellet beds
To improve heat and mass transfer characteristics of metal hydride
bed, it is proposed to augment the ETC of the bed. As discussed in our
previous article [18], using tin powder as the binder two different types
of pellets of Mg + 50 wt% LaNi4.6Al0.4 composite powder were de-
veloped. In the first type, Pellets of Composite Metal Hydride Powder
Fig. 3. PCI curves during absorption and desorption.
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Thermal Science and Engineering Progress 19 (2020) 100653
Fig. 4. van’t Hoff plot of Mg + 50 wt% LaNi4.6Al0.4.
and Graphite Flakes (PCMHPGF) (graphite flakes were supplied by
Sigma-Aldrich) was used to enhance the ETC. In addition to the gra-
phite flakes, in the second type of pellets, Pellets of Composite Metal
Hydride Powder Graphite Flakes with embedded Copper wire mesh
structure (PCMHPGFCu), a 3-D structure of copper wire mesh was
embedded. The structures were made from copper wire mesh instead of
copper sheet so that the advantage of high thermal conductivity of
copper can be utilized without losing much in terms of volume fraction
occupied by augmentation structure which do not add to hydrogen
absorption of the bed and thus impacts the effectiveness of hydrogen
sorption. Also fins were provided in an array on the periphery of the
said structure for improving the heat transfer in radial direction. The
pellets are depicted in Fig. 5. The ETC of the bed with powder com-
posite and pellets were measured at different hydrogen pressures and
concentration. A steady one dimensional radial heat conduction
method was used for the measurement of ETC. The Composite Metal
Hydride Bed (CMHB) was formed in the annulus of a cylinder made
with SS316 tube. A capsule heater was placed axially at the centre of
the CMHB; a cooling jacket was placed on the outer surface of the cy-
linder tube. The bed was heated at the centre using a capsule heater.
Circulating coolant through a cooling jacket the outer surface of the
cylinder was cooled. Thus one dimensional radial heat transfer is
achieved through the metal hydride bed by supplying predetermined
electric power to the heater and coolant at a fixed inlet temperature.
The lateral surface of the metal hydride bed was insulated to minimise
the lateral heat loss. Temperature of the metal hydride bed was mea-
sured radially at steady state. Thus from known electric power input to
the heater and measured temperature gradient of the metal hydride
bed, the ETC was calculated using Fourier equation. The details of the
ETC measurement cell, experimental procedure and data reduction are
given elsewhere [18]. Fig. 6 shows the variation of ETC with pressure
for all the three types of beds. The ETC of loose powder bed increased
from 0.5 to 1.5 W/m K with a rise in pressure. Its value almost got
saturated at a pressure of 15 bar, beyond which there is no significant
increase in ETC with increase in pressure. The range of pressure in
which increase in ETC observed is typically falls in the plateau region.
E. Anil Kumar, et al.
Fig. 5. (a) Pellets of Mg + 50 wt% LaNi4.6Al0.4 composite powder and graphite
flakes, (b) Pellets embedded with copper wire mesh structure, (c) Steps in Pellet
making (d) Dimensions of the Pellet.
Fig. 6. Variation of ETC with pressure with hydrogen as filling gas for
Mg + 50 wt% LaNi4.6Al0.4.
So that increase in ETC is also contributed by increase in gas con-
centration in the metal hydride. The inclusion of copper wire mesh
resulted in continuous heat conduction path in the radial direction.
Thus inclusion of copper wire mesh lead to enhancement in the heat
transfer in radial direction and consequently in the ETC. Using high
pressure for compaction with higher wt% of graphite flakes for making
metal hydride compacts will also increase the conduction path in the
radial direction, however it reduces the rate of hydrogen diffusion in
the metal hydride beds. Hence, it can be concluded that the compacts
made with mixture of metal alloy powder and graphite flakes and
embedded with copper wire mesh structure is a better method of ETC
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Thermal Science and Engineering Progress 19 (2020) 100653
augmentation for MH beds with minimal loss in hydrogen absorption
quantity [18]. A maximum ETC value of 8 W/mK, which is nearly 5
times higher than that of loose power bed, was observed in the case of
pellet with embedded copper wire mesh structure.
5. Measurement of absorption/desorption rates of metal hydride
beds
An experimental setup was fabricated for studying the hydrogen
absorption and desorption kinetics of three types of composite metal
hydride beds as shown in Fig. 7. The setup can be operated up to 60 bar
pressure. The setup was divided into 8 pre-calibrated volumes. A
combination of V5, V6, V7 (common for all experiments), and V1, V2, V3
and V4 volumes was used for supplying hydrogen. The amount of gas
absorbed and desorbed was calculated by measuring pressure drop and
rise in a known volume as a function of time. Fig. 8 shows the reactor
used for absorption and desorption kinetics measurement. The reactor
is made up of concentric SS cylinders. A sintered SS filter was used to
distribute hydrogen gas at the centre of the cylinder. Metal hydride bed
was formed in the inner annulus, heat transfer fluid is circulated in the
outer annulus. The complete fabrication details of experimental setup
and reactor are given elsewhere [19].
About 350 g of composite was used for measuring hydrogen ab-
sorption/desorption rates. After loading the material in the reactor, few
hydrogen absorption and desorption cycles were performed for the
activation of material. During absorption, bed temperature is main-
tained at 200 °C and hydrogen is supplied at 50 bar. During desorption
composite metal hydride bed was evacuated to vacuum pressure. After
activation of the composite, hydrogenation and dehydrogenation with
different bed temperatures, and hydrogen supply and discharge pres-
sures were performed. The temperatures for hydrogenation were
125 °C, 150 °C and 175 °C while temperatures for dehydrogenation
were 180 °C and 215 °C. The hydrogen supply pressure during hydro-
genation was kept constant at 20 bar.
To start the process of hydrogenation, heat transfer fluid at desired
temperature is circulated around the Composite Metal Hydride Bed
(CMHB) to raise its temperature to absorption temperature. Referring to
Fig. 7, hydrogen pressure is ensured by the pressure regulator and the
tubes downstream of regulator are filled with hydrogen at the desired
supply pressure. Hydrogen at appropriate pressure is supplied to the
CMHB by opening the valve v8. This is continued to ensure that the
equilibrium pressure of CMHB gets equal to the hydrogen supply
pressure. The heat transfer fluid flowing at constant inlet temperature
carries away the heat of absorption. The temperatures at three different
locations in CMHB, as well as the temperatures of heat transfer fluid at
inlet and outlet and pressures at different locations are recorded in time
intervals of 2 s using a data acquisition system. At the end of hydro-
genation process, valve v8 is closed.
During the dehydrogenation or charging process the temperature of
thermostatic fluid is raised to the temperature at which the CMHB has
to desorb hydrogen. This fluid is then circulated through the thermo-
static fluid jacket, enveloping the Composite Metal Hydride (CMH)
reactor. When the average bed temperature achieves thermal equili-
brium with the thermostatic fluid, valves v9 and v10 are opened and
hydrogen released from the CMHB is stored in the hydrogen storage
cylinder till the pressure between the CMH reactor and the storage
cylinder gets equalized.
The masses of hydrogen absorbed and desorbed in the above pro-
cesses are calculated as described by the authors [19].
6. Results and discussion
As discussed earlier, the Mg + 50 wt% LaNi4.6Al0.4 composite was
selected for the application of MHTES due to its favourable thermo-
dynamic properties and better absorption/desorption kinetics com-
pared to pure magnesium hydride. Encouraged with the improvement
E. Anil Kumar, et al. Thermal Science and Engineering Progress 19 (2020) 100653

Fig. 7. Experimental setup for measurement of hydrogen absorption and desorption kinetics.

in sorption kinetics obtained by applying the ETC augmentation tech-

niques in our previous work [19], the same augmentation techniques
were also applied in the present work, for the application of MHTES.
Following sections discuss the effect of ETC augmentation on the
sorption kinetics of Mg + 50 wt% LaNi4.6Al0.4 composite hydride bed.

6.1. Effect of ETC augmentation on hydrogen absorption rates

The hydrogen absorption kinetics of three configurations of com-

Fig. 8. Reactor for measurement of hydrogen absorption and desorption ki-
netics.
posite metal hydride beds, namely, with Loose Composite Metal
Hydride Powder (LCMHP), Pellets of Composite Metal Hydride Powder
and Graphite Flakes (PCMHPGF), and Pellets of Composite Metal
Hydride Powder Graphite Flakes with embedded Copper wire mesh
structure (PCMHPGFCu), were measured at three different absorption
temperatures (125 °C, 150 °C and 175 °C). The results are depicted in
Fig. 9(a)–(c).
The rate and amount of hydrogen absorbed by a metal hydride bed
are generally dependent on the pressure at which the hydrogen is
supplied and the average temperature achieved by the bed. If the supply
pressure of hydrogen is maintained constant, heat transfer parameters
will be the decisive factors for the variation of average temperature in
the bed with time. It is a well-known fact about the metal hydride beds
that the mass and heat transfer regulate the sorption kinetics. In case of
Mg based materials, the absorption capacity increases with increase in
temperature up to 200 °C. Among the three types of CMH beds dis-
cussed above, since the surface area of exposure is comparatively more
in the case of powder bed, the hydrogen can diffuse faster in the be-
ginning, for a given hydrogen supply pressure. The time period for
which the powder bed will exhibit faster absorption depends on the

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E. Anil Kumar, et al. Thermal Science and Engineering Progress 19 (2020) 100653

to influence the average bed temperature. Poor thermal conductivity

results in inappropriate heat dissipation from the bed. A consequence of
this will obviously be a sudden rise in the temperature in the bed. This
further results in slower sorption. If we divide the graph of absorption
kinetics (shown in Fig. 9) into three regimes comprising first 100 s,
100–300 s and beyond 300 s, we can see that for LCMHP bed, first
regime shows rapid absorption of hydrogen accompanied with similar
rise in temperature. In the second regime, the average bed temperature
becomes very high because of poor heat transfer characteristics leading
to decrease in the rate of hydrogen absorption. In the third regime, the
hydrogen absorption is minimal. The other two types of beds
(PCMHPGF and PCMHPGFCu) exhibit different trends. After showing
slightly slower absorption in the first phase, the absorption improves in
the second phase with a lower rise in temperature. This is because of
better heat dissipation from these beds which has resulted due to
augmentation of ETC. The average bed temperature profiles suggests
the ease of heat transfer within the bed. The maximum temperature rise
in case of LCMHP were 75 °C, 76 °C and 79 °C for absorption tem-
peratures of 125 °C, 150 °C and 175 °C respectively, the respective
temperature rises for PCMHPGF bed were 63 °C, 67 °C and 50 °C and
those for PCMHPGFCu bed were 58 °C, 60 °C and 45 °C respectively.
This clearly shows the improvement in heat transfer characteristics
achieved by the ETC augmentation techniques. As the rise in tem-
perature of thermostatic fluid will be similar to the rise in average bed
temperature, in case of LCMHP, thermal energy is recovered at a higher
temperature compared to composite metal hydride beds with aug-
mentation. For a particular absorption temperature, the rate of ab-
sorption is also high in case of powder bed. However, due to poor heat
transfer characteristics, the time taken for the bed to reach initial
temperature is higher. As can be seen from Fig. 9(a)–(c), as the ab-
sorption temperature (thermostatic fluid inlet temperature) increases,
the rate of hydrogen absorption increases and this leads to reduction in
time required for the composite metal hydride bed to reach saturation.
The amount and rate of hydrogen absorption increases with tempera-
ture up to a certain value in case of Mg based materials. The mixing of
LaNi4.6Al0.4 although causes better hydrogen absorption at lower tem-
peratures but studies suggest that with increase in absorption tem-
perature, the hydrogen absorption characteristics (both, rate as well as
quantity of absorption) show improvement [16]. This is true for all the
three configurations of beds. The time required for the LCMHP bed to
reach the saturation stage were 400 s, 360 s and 330 s respectively for
absorption temperatures of 125 °C, 150 °C and 175 °C, while the time
recorded for the PCMHPGF bed were 280 s, 180 s and 160 s and those
for PCMHPGFCu were 195 s, 150 s and 120 s. As the increase in hy-
drogen absorption rate, the rate of heat release increases, the tem-
perature rise is greater at higher temperatures.

6.2. Effect of ETC augmentation on hydrogen desorption rates

The hydrogen desorption experiments were conducted at two tem-

peratures, 180 °C and 215 °C. From Fig. 10(a), (b), it is evident that the
Fig. 9. Hydrogen absorbed and bed temperature for absorption (supply pres-
sure = 20 bar): (a) Thermostatic fluid inlet temp = 125 °C, (b) Thermostatic
increase in desorption temperature resulted in better desorption rates.
fluid inlet temp = 150 °C, (c) Thermostatic fluid inlet temp = 175 °C. Similar to absorption, in case of desorption, the time required for
maximum hydrogen desorption decreased with increase in desorption
temperature. For LCMHP bed, the time required for achieving max-
hydrogen supply pressure. In case of beds of pellets, because of some
imum hydrogen desorption was 200 s for 180 °C desorption tempera-
reduction in the exposed surface area, hydrogen faces resistance to
ture, it was 150 s for the desorption temperature of 215 °C. This sug-
diffusion and thus the absorption rate would be lower initially.
gests that the desorption kinetics gets faster with increase in desorption
Therefore, the initial rate of hydrogen absorption will be more for
temperature. Following the same trend, the time required for desorbing
powder bed irrespective of the supply pressure. Faster hydrogen ab-
maximum amount of hydrogen, decreased from 100 s/75 s to 75 s/50 s
sorption results in higher heat release rates and consequently the
for PCMHPGF/PCMHPGFCu beds respectively for 180 °C and 215 °C
average temperature of the bed rises in this regime for powder bed. The
desorption temperatures. While the maximum amount of hydrogen
kinetics of sorption for CMH beds also depends on average temperature
desorbed by the LCMHP bed was 88% (of total absorbed hydrogen),
prevailing in the bed and the pressure gradient available for supplied
when the desorption temperature was 180 °C, this quantity increased to
hydrogen, in addition to hydrogen diffusion through the formed hy-
90% for 215 °C desorption temperature. Similarly, for PCMHPGF and
dride phase [20–24]. ETC of the bed is one of the important parameters
PCMHPGFCu beds the quantity of hydrogen desorbed increased from

6
E. Anil Kumar, et al.
Fig. 10. Variation of amount of hydrogen desorbed and average bed tempera-
ture during desorption: (a) Thermostatic fluid inlet temp = 180 °C, (b)
Thermostatic fluid inlet temp = 215 °C.
90 to 92%, when the desorption temperature was increased from 180 to
215 °C. The effect of ETC augmentation can be clearly observed for both
the desorption temperatures. Compared to absorption process, the ef-
fect of augmentation is better for desorption process as far as average
bed temperature variation is concerned. Verifying the reasoning given
in the previous section, the implementation of ETC augmentation
techniques have resulted in more uniform bed temperature during
desorption process. The minimum temperatures in case of LCMHP bed
for desorption temperatures of 180 °C and 215 °C were 117 °C and
158 °C respectively while these temperatures for PCMHPGF/PCMHP-
GFCu were recorded as 151 and 191 °C/156 °C and 193.5 °C. The higher
the minimum temperature the better the heat transfer through the bed.
Better heat transfer through the bed will lead to better heat energy
utilization from the thermal energy source i.e. better functioning of
MHTES system. Hydrogen desorption characteristics also got improved
with the implementation of ETC augmentation techniques as ETC
augmentation resulted in improvement in both the quantity and the
rate of hydrogen desorption. While the LCMHP desorbed around 88% of
hydrogen, PCMHPGF and PCMHPGFCu recorded desorption of around
91% for the same desorption and absorption temperatures. Also, the
time taken for powder bed to reach saturation stage was 220 s whereas
this was around 100 s for pellet beds. Similar to absorption kinetics,
better rate of hydrogen desorption will result in decrease in the process
time for MHTES system. Maximum errors in the estimation of amount
of hydrogen absorbed and amount of hydrogen desorbed were found to
7
Thermal Science and Engineering Progress 19 (2020) 100653
be ± 3.95% and ± 4.6% respectively.
7. Conclusions
A composite of Mg + 50 wt% LaNi4.6Al0.4 was tested for hydrogen
absorption and desoption characteristics in three different bed config-
urations, Loose Composite Metal Hydride Powder (LCMHP), Pellets of
Composite Metal Hydride Powder and Graphite Flakes (PCMHPGF) and
Pellets of Composite Metal Hydride Poweder, Graphite Flakes with
embedded Copper wire mesh structure (PCMHPGFCu), at various sets
of operating conditions. The following conclusions are drawn from this
work:
1. LCMHP bed shows higher rate of hydrogen absorption in the initial
phase owing to the relatively larger surface area of exposure and
lesser resistance experienced by the hydrogen molecules in this case.
However, considering the overall performance, saturation stage is
reached faster by the beds of pellets as these beds have better heat
transfer characteristics.
2. The two types of beds of pellets, PCMHPGF and PCMHPGFCu ex-
hibit lower temperature drop compared to that for LCMHP bed
which confirms the improvement in heat transfer to and from the
bed.
3. The minimum temperatures in case of Mg + 50 wt% LaNi4.6Al0.4
powder bed for desorption temperatures of 180 °C and 215 °C were
117 °C and 158 °C respectively while these temperatures for
PCMHPGF/PCMHPGFCu were recorded as 151 °C and 191 °C/
156 °C and 193 °C respectively.
4. While the Mg + 50 wt% LaNi4.6Al0.4 powder bed desorbed around
88% of hydrogen, the beds of pellets desorbed around 91% at the
same desorption and absorption temperatures.
5. The pelletization and inclusion of three-dimensional copper mesh
structure improved the heat transfer characteristics of the composite
metal hydride bed thereby leading to better sorption characteristics.
CRediT authorship contribution statement
E. Anil Kumar: Conceptualization, Methodology, Supervision,
Project administration, Funding acquisition. Yogesh Madaria:
Investigation, Data curation, Writing - original draft. K. Sarath Babu:
Visualization. S. Srinivasa Murthy: Supervision, Writing - review &
editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
One of the authors, E. Anil Kumar, acknowledges Department of
Science&Technology, Government of India for funding the project vide
Project No. DST/TMD/MES/2k16/50.
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