Nano Energy (2012) 1, 566–589

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REVIEW

High capacity hydrogen storage: Basic aspects,

new developments and milestones
D. Pukazhselvan, Vinod Kumar, S.K. Singhn

Hydrogen Energy Lab, Department of Physics, Deenbandhu Chhotu Ram University of Science and Technology,
Murthal, Sonepat, Haryana 131039, India

Received 31 March 2012; received in revised form 10 May 2012; accepted 10 May 2012
Available online 23 May 2012

KEYWORDS Abstract
Hydrogen economy; One of the major technical bottlenecks in hydrogen economy is hydrogen storage. None of the
Hydrogen storage; hydrogen absorption materials known today exclusively meets all the required properties such
Complex hydrides; as storage capacity (4.5 wt%), reaction enthalpy (15–24 kJ/mol), kinetics (0.02 g H2/s), cycle
Nanocatalysis life (410,000 cycles), desorption temperature (o100 1C), etc. However, there are striking
recent developments; as for example, development of reactive hydride composites (RHC),
nanoconfinement of hydrides by nanoscaffold materials, synthesis of new generation alkali–
alkaline earth composite structures and air stable nanocomposite system, etc. All these
materials are conceptually interesting candidates, but when it comes to practical reality, still
significant problems need to be circumvented. The present review therefore attempts to throw
some insight on almost all classes of known hydrogen storage materials. The very basic aspects
of hydrogen storage are presented and the promise of state of the art candidates is indicated.
& 2012 Elsevier Ltd. All rights reserved.

Introduction environmental implications [4]. This is due to the fact that

renewables are season/location sensitive and nuclear fuels
Sustainable clean energy development is the most compel- are not safe. Hydrogen is very advantageous in the sense
ling need of the world today. In quest of developing that (a) it is a clean burning fuel, (b) it possesses higher
sustainable clean energy, many alternative options such as energy content per mass unit and (c) it is the only
renewable energy (wind, solar, tidal, geothermal energy), indigenous energy carrier existing all over the world. Never-
nuclear energy and hydrogen energy are extensively dis- theless, in spite of all such merits, a flawless economic
cussed. From the insight gained from many in-depth reviews system based upon H2 fuel (hydrogen economy) could not be
[1–3] it appears to be that hydrogen is the best option to readily framed due to a couple of technical challenges in
curb out a balanced energy mix without prompting areas such as hydrogen production, storage and application,
etc. Among these three areas hydrogen storage presents a
huge challenge. It was proposed by USDOE [5] that a
n
Corresponding author. Tel.: +911302484136; fax: +911302484004. hydrogen storage media with 4.5 wt% reversible hydrogen
E-mail address: sksingh2k6@[Link] (S.K. Singh). capacity under affordable conditions should be established

2211-2855/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
[Link]
High capacity hydrogen storage 567

for commercial applications (the USDOE’s earlier target was combustion of hydrogen is almost three times higher as
6 wt% gravimetric density, which was later revised to compared to the LHV of gasoline.
4.5 wt%). Both high compression storage and cryogenic
C8H18 + 12.5O2-8CO2 +9H2O (LHV =45 kJ/g) (1)
storage modes are considered ineffective due to high cost
and safety concerns. Thus the effective means of hydrogen
storage system appears to be reversible metal hydrides. Many H2 +½O2-H2O (LHV =120 kJ/g) (2)
metal hydrides have so far been investigated but none of the
materials offer the required benchmark performances for Hydrogen combines with oxygen to form water and
onboard storage applications. High capacity light weight generates electricity in fuel cells (cold combustion) and it
hydrides are therefore paid much attention; however, sig- can also be burnt inside the internal combustion engines
nificant technical challenges needs to be circumvented. or turbines (hot combustion) to power devices and motive
After decades of extensive investigation, it is now con- systems. Some of the key properties of hydrogen are
cluded that a storage capacity of above 4.5 wt% can be compared with methane and gasoline fuels in Table 1 [13].
achieved only through light weight materials, particularly The table clearly illustrates that hydrogen is the potential
with elements having atomic number of up to 20 [6–8]. In alternative to the conventional hydrocarbon fuels. Never-
fact, an exhausting list of high capacity hydrogen storage theless, it is necessary to note that hydrogen is not a fuel by
materials is known with capacity even more than double the source, but is an energy carrier i.e. hydrogen must be
required 4.5 wt%. But, these hydrides are either too stable initially procured to proceed with reaction (2). For under-
or too unstable and not reversible under the ideal operating standing the number of ways practiced for producing
conditions [9]. Therefore research efforts like catalyzing hydrogen, the reader is referred to reviews in Ref. [14].
high capacity hydrides, decorating/doping the selected sites In-depth discussion regarding hydrogen production is beyond
for tuning the properties, chemical modification for enhan- the scope of the present review.
cing the thermodynamic features and tailoring of new light Due to the low density of hydrogen, storage of hydrogen
weight composite systems have been attempted in recent under ambient condition requires a huge volume (11.2 l for
years [10–12]. The present review illustrates some of the 1 g of hydrogen). High pressure storage is widely discarded
interesting hydrogen storage candidates with special refer- since it is risky, cost-intensive and highly ineffective. In the
ence to hydrides formed by elements with atomic number case of cryogenic storage, the low temperature require-
less than 20. We initially address the basic aspects of ment (o253 1C) for liquefaction and the requirement of
hydrogen storage, simple thermodynamic considerations super insulated containers make this mode very expensive.
and the unique features of catalysts in metal–hydrogen Handling and distribution of liquid hydrogen is also a
interaction, etc. A brief overview of recent developments difficult talk. Liquid hydrogen cannot easily be moved via
in a variety of hydrogen storage materials is sequentially underground pipelines and it is necessary to use special
indicated. We finally discussed the new interesting strate- vacuum insulated hoses for moving liquid hydrogen from
gies employed by various researchers for improving the container to container. Thus, this option is not easily
hydrogen storage capacity of state of the art materials. practicable [15]. The reversible reaction of hydrogen with
metals, alloys or intermetallic compounds is considered as a
convenient way of storing hydrogen [16]. This is due to the
Hydrogen fuel for transport applications fact that, unit volume of a metal hydride holds more
hydrogen than liquid hydrogen does.
Hydrocarbon fuels consume oxygen and releases carbon The U.S. Department of Energy (DOE), in consultation
dioxide during the combustion reaction, thereby largely with the U.S. Council for Automotive Research (USCAR), has
disturbing the oxygen to carbon dioxide ratio in the atmo- established an evolving set of technical targets for the on-
sphere. The combustion reaction of hydrogen is quite board hydrogen storage systems which is shown in Table 2.
neutral because the consumed oxygen again gets released The previous set of these targets was established in 2003
during the production of hydrogen from the product [17]. The targets set out in the previous reports for
(water). Moreover, the lower heating value (LHV) of the establishing a hydrogen storage material with 9 wt% by

Table 1 Comparison of few important properties of hydrogen with hydrocarbon fuels such as gasoline and methane.

Properties Unit Hydrogen (H2) Methane (CH4) Gasoline (C8H18)

Energy content kWh/kg 33.33 13.9 12.4

Self ignition temperature 1C 585 540 228–501
Flame temperature (in air) 1C 2130 1960 1977
Flame temperature (in O2) 1C 2810 2780 2200
Ignition limits in air vol% 4–75 5.3–15 1.0–7.6
Min. ignition energy mW s 0.02 0.29 0.24
Flame propagation in air m/s 2.65 0.4 0.4
Detonation limits vol% 13–65 6.3–13.5 1.1–3.3
Detonation velocity km/s 1.48–2.15 1.39–1.64 1.4–1.7
Explosion energy vol% 13–65 6.3–13.5 1.1–3.3
568 D. Pukazhselvan et al.

Table 2 The hydrogen commercialization target as set out by USDOE. The old and revised targets are given.

Storage parameter Units Old targets (2003) New targets (2009)

2010 2015 2010 2015 Ultimate

kWh/kg 2 3 1.5 1.8 2.5

Gravimetric capacity wt% H2 6 9 4.5 5.5 7.5
kWh/L 1.5 2.7 0.9 1.3 2.3
Volumetric capacity gH2/L 45 81 28 40 70
Delivery temp. 1C –40/85 –40/85 –40/85 –40/85 40/95–100
Pressure MPa (min/max) 0.4/10 0.3/10 0.5/1.20 0.5/1.20 0.3/1.20
Kinetics (gH2/s)/kW 0.02 0.02 0.02 0.02 0.02
Cost $/kW net 4 2 To be determined

2010 did not become a reality. A revised set (US:DOE—EERE,

2010) of targets [5] was therefore introduced in early 2009
which is also shown in the table.

Metal hydrides

Interaction of hydrogen with solid surfaces

Storage of hydrogen in molecular form and/or atomic form

can be achieved depend on the binding energy between the
metal adsorbents and hydrogen. During metal-hydrogen inter-
action, heat is either absorbed (endothermic) or released
(exothermic) [18,19]. Therefore the metal hydrides are often
considered as excellent heat storage systems also [20]. A
typical metal–hydrogen reaction can be written as [21]
x Figure 1 Simple potential energy diagram for interaction of
Mþ H2 -MHx ð3Þ hydrogen with metal surfaces.
2
Source: Hydrogen as a Future Energy Carrier, Edited by Zuttel,
The interaction of hydrogen with metals takes place with 2008) [25].
a sequence of surface interactions between the H2 mole-
cules and the metal atoms [22]. The sequence of interac-
tions can be visualized with the help of a potential energy
Chemisorption
diagram shown in Figure 1. The potential energy curve for
Chemisorption is an activated process, which means energy
hydrogen approaching a solid surface typically shows two
is required to break the bond of hydrogen molecules. Due to
energy minima with different depths; one at greater
the existence of activation energy barrier, this interaction
distance from the adsorbent (corresponds to physical
exhibits slower kinetics than physisorption. If no barrier is
adsorption) and the other at smaller distances. The latter
found, the molecule approaches the surface easily and
interaction which shows a deeper minimum corresponds to
dissociates into atoms straightforwardly. If the barrier is
the real chemical interaction (Figure 1) between hydrogen
large, the reactants are required to be activated, either by
and metal atoms.
performing the reaction at higher temperature or by
introducing catalysts. The barrier is typical for the late
Physisorption transition metals and especially for the noble metals and
The physical adsorption of hydrogen on a metal surface is the so-called free electron metals where there is no
caused by weak Van der Waals forces between the hydrogen d-electron to facilitate the reaction. For in-depth analysis
molecules and metal surface. This is composed of an of metal–hydrogen interaction with clear potential energy
attractive term and a repulsive term and the combination curve calculations upon a number of metal–hydrogen system
of these gives rise to a shallow minimum in the potential the reader is referred to the work of Hammer and Narskov
energy curve at a distance of approximately one molecular [23,24]. In principle, the required condition for the H–H
radius with the interaction energy typically 1–10 kJ/mol H2. bond dissociation energy is DHMH +Ea. (i.e. Z436 kJ/mol
This small energy is not sufficient to cause bond breaking; H2). If the height of the barrier is very high and the
hence the gas is adsorbed in its molecular form. As the potential well is small, less stable hydride gets formed but
forces involved in this interaction are very weak, physisorp- the reaction has to be performed at higher temperature.
tion usually takes place only at low temperatures. Moreover, Conversely, if the height of the barrier is less and the
since no activation energy barrier is involved in physisorp- potential well is high, very stable hydrides get formed with
tion, this process usually occurs with fast kinetics. rapid hydriding kinetics.
High capacity hydrogen storage 569

phase transformation is given by the van’t Hoff law [22]:

DH DS
ln Peq ¼  þ ð5Þ
RT R
The enthalpy of formation of the hydride is calculated
from the slope of the straight line obtained by plotting
ln PH2 versus 1/T. As the entropy change corresponds mostly
to the change from molecular hydrogen gas to dissolved
hydrogen in metals, the value of entropy for metal–
hydrogen interaction is 130 J/K mol H2.

Role of catalysts in metal–hydrogen reaction

Due to the existence of activation energy barrier in metal–

hydrogen reaction pathways, catalysts play a prominent
role. The catalytic component does not change the basic
thermodynamics of M–H system, but enhances the rate of
Figure 2 Pressure–Composition–Temperature diagram (PCT iso-
the reaction. Since the incorporation of external catalysts
therms). Inset: van’t Hoff plot.
enhances the total weight of the sample, the amount of
catalyst should be kept as little as possible. The efficiency
The thermodynamic features can be explained by PCT of the catalyst depends critically on how well it is dispersed
isotherms [25]. A representative picture of PCT isotherm throughout the system. Therefore, in solid–hydrogen reac-
and van’t Hoff diagram are shown in Figure 2. When tions, it is desirable that the employed catalyst is in nano-
hydrogen absorbing materials are exposed to hydrogen form so as to increase catalyst–reactant contact area [26].
atmosphere, hydrogen atoms slowly gets dissolved in the In the case of intermetallic hydrides the catalytic species
metal and forms a solid solution phase (a phase). In this present at the surface facilitates easy bond breaking/
phase hydrogen is randomly distributed in the interstitial formation and triggers rapid hydrogen absorption/deso-
sites and the concentration increases slowly with pressure. rption reaction. However intermetallic hydrides at present
At a particular pressure and concentration of a phase, are not considered promising due to their poor gravimetric
nucleation of a higher concentration phase (b phase) occurs. hydrogen storage capacity. The light weight, hydrogen rich
The full system now has three phases (a, b and hydrogen compounds like MgH2, NaAlH4, etc. are promising candi-
gas) and two components (metal and hydrogen). The dates but the pristine material surface exhibits very poor
pressure at which this transformation takes place is referred catalytic activity [27,28]. The role of catalysts in metal–
as the plateau pressure and in this region the a-phase and hydrogen reaction has been extensively reviewed by many
b-phase co-exist. At this pressure hydrogen occupy the researchers [29–31]. Grochala and Edwards [32] have classi-
interstitial sites more rapidly until the depletion of a-phase. fied the high capacity light weight metal hydrides into three
The moment a-phase disappears, the pressure rises up categories (Figure 3), namely
again, this is called the solution phase of metal hydride.
The plateau pressure at any given temperature provides us  Thermodynamically less stable/unstable hydrogen sto-
the valuable information about the stability of the hydride. rage materials with low activation energy barrier and
The formation of phases in metal hydride reaction can be lower desorption temperature, which stores hydrogen
readily explained by Gibb’s phase rule. According to this irreversibly (e.g., AlH3 [33], curve A)
rule  Thermodynamically very stable hydrogen storage mate-
f ¼ CP þ2 ð4Þ rials with high activation energy barrier and higher
desorption temperature, which stores hydrogen reversi-
where f—degrees of freedom, C—number of components bly (e.g., MgH2 [34], curve B).
and P—number of phases.  Thermodynamically slightly stable hydrogen storage
At the mixed phase region (i.e. the plateau pressure materials with intermediate desorption temperature
region) the total number of phases of the system is three and activation energy barrier, which stores hydrogen
(a, b and hydrogen gas), and the total number of compo- irreversibly (e.g., LiAlH4 [35], curve C).
nents are two (metal and hydrogen). The system possesses
only one degree of freedom. Thus only hydrogen concentra-
tion increases with the depletion of a-phase at a constant Reviewing upon these three classes of hydrogen storage
pressure. When a-phase is fully depleted, since one addi- systems (A, B and C), it is clearly understood that all these
tional degree of freedom is regained, the hydrogen con- three systems do not solve the problems of on-board hydro-
centration also increases (b-phase) with the increase in gen storage because of the high stability of reversible
hydrogen pressure. Stable hydrides (DHf50) will require hydrides and irreversible characteristics of less stable
higher temperatures than less stable hydrides (DHfo0) to hydrides. However, optimum hydrogen-storage characteris-
reach a certain plateau pressure. By making series of PCI’s tics may be reached exclusively in a catalytically enhanced
at different temperatures, it is even possible to construct a system. Figure 3 is the pictorial representation of these three
phase diagram from the end points of the plateaus in the classes of hydrides. The reaction coordinate at point x1
individual PCI’s. The equilibrium pressure Peq at the a-b represents irreversibility and x2 represents reversibility. The
570 D. Pukazhselvan et al.

detailed description regarding the rules for selection of A

and B can be seen in the report of Anderson and the
references discussed therein [39]. In general, ‘‘A’’ corre-
sponds to metals which make stable binary hydride when
exposed to hydrogen and ‘‘B’’ corresponds to a transition
metal which can only make less stable or unstable binary
hydride. AB5-type intermetallic system reacts with hydro-
gen to form ternary metal hydrides. The main advantage
of AB5 intermetallic system for hydrogen storage is that
it absorbs and liberates hydrogen under nearly ambient
conditions [40]. The archetype and most thoroughly inves-
tigated among these alloys is LaNi5. It reacts rapidly with
hydrogen at STP conditions following the reaction:
LaNi5 +3H22LaNi5H6 (6)

When hydrogen atoms react with LaNi5 surface, hydrogen

molecules get dissociated to hydrogen atoms and are then
chemisorbed in the bulk structure of LaNi5 to make LaNi5H6.
The catalytic activity for breaking the hydrogen molecules
Figure 3 Schematic ‘‘energy vs. reaction coordinates’’ dia- to hydrogen atoms is provided by Ni clusters present at the
gram classifying the four different catagories of hydrides with surface of LaNi5. In the case of LaNi5 intermetallic system
respect to stability and activation energy barrier for forward/ the surface layer consists of Ni clusters and La2O3 formed
reverse reactions. Adapted with permission from Ref. [32], through the following reaction [41]:
Copyright& (2004) American Chemical Society. 2LaNi5 +3/2O2-La2O3 +10Ni (7)

main problem associated with these hydrides (cases A, B and C) Few examples of other classes of intermetallic system are
is the high activation energy barrier either during forward summarized in Table 3 and the details of these materials
reaction pathway or in reverse pathway. The activation can be seen in the references given therein. It should be
energy barrier can be decreased by catalysis. A targeted mentioned that intermetallic systems are the oldest and
situation (see curve D) can therefore be reached by widely investigated systems for device applications. It is
catalyzing/doping thermodynamically slightly stable hydro- now clear that due to the insufficient weight per unit
gen storage materials for storing hydrogen reversibly under volume of hydrogen, this system cannot meet the targets
moderate operating conditions (vertical arrows symbolize for mobile applications. However, for stationary applica-
the activation barrier for the decomposition). There has tions (as for example, large underground cylinders in
been much progress recently in the catalytic enhancement hydrogen production spots, refueling stations, residential
of reversibility [36] with concomitant lowering of desorption blocks, etc.), intermetallic hydrides are very useful because
temperature for a certain group of hydrides. One of the key weight is not a problem here [52,53].
groups of catalytically enhanced system is alanates with
particular reference to Sodium Alanate (NaAlH4) [37,38].
Light weight binary hydrides and their composites
Brief description of nanocatalysis for this system is given in
the Section ‘‘Complex aluminum hydrides’’.
Most of the metals in the periodic table form binary hydrides
[54]. The in-depth reviews of Beavis, Bouten and Miedema,
General classification of metal hydrides and Christmann give the detailed description regarding the
binary metal hydrides [22,55,56]. Among all the binary metal
Metal hydrides can be classified into four broad categories hydrides, few metal hydrides such as MgH2, AlH3 and PdH2
such as intermetallic hydrides, light weight binary metal have received much attention. Magnesium hydride is a
hydrides, large surface area materials and complex metal reversible hydride even in the absence of catalysts. The
hydrides. In addition to this, amino borane, amide/imide work of Tanguy et al. [57] is one of the earliest works
system, liquid hydrides, microspheres, etc. have also performed on Mg–H system which paved the way for the wide
recently become the emerging class of hydrogen storage investigation of Mg based system. Magnesium reacts with
systems. The following section overviews the interesting hydrogen according to the following reaction:
hydrogen storage candidates which falls in these categories.
Mg + H2-MgH2 (8)

Intermetallic hydrides The amount of hydrogen stored corresponds to 7.6 wt%

and the plateau pressure of 1 atm occurs at temperatures
Intermetallic hydrides, also called interstitial hydrides, are around 300 1C. The desorption kinetics at this temperature
grouped into four broad categories, such as AB5, AB, A2B and is slow. Thus, temperature in excess of 400 1C is required for
AB2. Few archetype materials of these classes is shown in faster desorption kinetics [58]. In a recent study conducted
Table 3. The choice of the materials for A and B is based by Wronski et al. [59], it was shown that nano Ni powder is
upon the stability criteria (rule of reversed stability). The a promising catalyst for MgH2. They have reported high
High capacity hydrogen storage 571

Table 3 Classification of intermetallic system for hydrogen storage and few archetype metals of this class.

Properties AB5 AB A2B AB2

Specific example LaNi5 FeTi Mg2Ni TiMn2

Temperature Room temp Near room temp. 300 1C Near room temp.
Storage capacity (wt%) 1.43 1.75 3.8 1.7
Structure Hexagonal Cubic Cubic Hexagonal or cubic
References [42–44] [45–46] [47–49] [50–51]

Figure 5 The three step chemical processing for the regen-

eration of AlH3 from the spent hydride. Reproduced with
permission from Ref. [79], Copyright& (2011) Elsevier.

Figure 4b) using the metal incorporated SWCNT catalyst.

These studies suggest that catalyzed MgH2 system is also a
probable candidate for fueling a high temperature fuel cell.
However, it should also be kept in mind that, from thermo-
dynamic point of view, the binary Mg–H system did not yet
fall within the range of USDOE target. Therefore, in search
Figure 4 (a) Desorption kinetics of MgH2 system catalytically for viable storage materials with high capacity, recourse was
enhanced by metal incorporated SWCNT (‘‘ap’’ stands for the taken to Mg-based alloy systems. Nagai et al., Raman et al.
as-prepared SWCNT with Fe, Co, Ni impurities. ‘‘ps’’ stands for and many others [61–66] have studied composite systems
the metal free SWCNT. FeCoNi stands the SWCNT excluded comprising of Mg together with AB5/AB/AB2 ingredients and
system) and (b) The hydrogen absorption kinetics at 150 1C and reported enhanced absorption/desorption performances.
20 atm. Adapted with permission from Ref. [60], Copyright& Recently, Kim et al. [66] have shown that the new composite
(2005) American Chemical Society. Mg–20 wt% ZrFe2 prepared through hydriding combustion
synthesis (HCS) route rapidly absorbs 5.7 wt% at 300 1C
desorption–reabsorption kinetics, lowering of activation and the capacity is very consistent during long term cycling
energy by almost 50% and decrease in dehydrogenation runs. Czujko et al. have studied the composite mixtures of
temperature by about 100 1C. Recently, Wu et al. [60] have MgH2–LiAlH4 and NaBH4–MgH2 hydrides prepared by mechan-
shown that metals incorporated SWCNT catalyst dramati- ical milling method [67]. It was shown that the peak
cally improve the hydrogen absorption/desorption charac- hydrogen desorption temperature (i.e., temperature for
teristics of MgH2 system. As seen in Figure 4 a 5 wt% metal highest desorption rate) of the MgH2 constituent in the
incorporated (where 2 wt% is composed of Fe, Co and Ni MgH2 +LiAlH4 composite decreases linearly with increasing
metals) SWCNT triggers 6 wt% hydrogen within 25 min at weight fraction of complex hydride component, whereas
300 1C. This kinetics is much superior to pristine system, peak desorption temperature of NaBH4 decreases dramati-
purified SWCNT added system and the separate Fe, Co and cally with increasing amount of MgH2 in the composites.
Ni metals added system. The dehydrogenated material Another interesting light weight binary hydride is Alumi-
reversibly stores the full capacity within an hour at the num hydride (AlH3) which is a covalently bonded, meta-
temperature of 150 1C under 20 atm hydrogen (see stable solid at room temperature with a large gravimetric
572 D. Pukazhselvan et al.

and volumetric hydrogen capacity (10.1 wt% and 149 kg/m3, pressures and temperatures. They evaluated the optimum
respectively) [68,69]. AlH3 was originally synthesized as a adsorbent structures that would enable high adsorptive prop-
nonsolvated solid using an organometallic synthesis route by erty by modifying both the tube diameters and the inter-tube
Brower et al. [70]. The initially known AlH3 was a-AlH3 spacing under different thermodynamic conditions. It must be
[71–73]. In later stages, Brower et al. successfully prepared recognized that theoretical approaches [86] have given more
six other non-solvated AlH3 polymorphs, i.e a, b, g, d, e, and coherent results than experiments whose data are relatively
z. AlH3 is actually a metastable hydride at room tempera- scattered and even contradictory. As per the view of Darkrim
ture, however, by the Al oxide layer that covers the AlH3 et al. [87], one of the reasons for the contradictory experi-
matrix, AlH3 can be maintained intact under ambient ential results over theoretical predictions is that the basic
conditions. A team of Brookhavan National Laboratory material is different in these two cases. The nanotubes
[74,75] has extensively studied the synthesis, catalysis, considered in molecular simulations are open tubes, well
thermodynamics and kinetic characteristics of AlH3. The structured, without amorphous carbon and impurities, having
thermal decomposition reaction of the AlH3 polymorphs is well determined-chosen diameters and geometrical location in
quite straightforward as shown below the bundles. On the contrary, because of difficulties in
synthesis and purification, the nanotubes samples used, up
AlH3-Al+3/2H2 (9)
to date, in experimental investigations are not of high purity,
containing amorphous carbon and several impurities (generally
Graetz et al. have prepared polymorphs of AlH3 by
catalytic residues resulting from their synthesis). Some typical
organometallic synthesis. It was shown that a freshly
carbon nanostructures and the corresponding hydrogen sto-
synthesized, non-solvated AlH3 releases approximately
rage capacity and operating conditions are summarized in
10 wt% H2 at desorption temperatures 100 1C. They also
Table 4.
report that the H2 evolution rates for small crystallites of a
In a topical review of Liu and Cheung [95] a wide class of
and g-AlH3 (undoped) meet the DOE full flow target for a
carbon nanomaterials, both pure and metal decorated
50 kW fuel cell (1 g H2/s) above 114 1C (based on 100 kg
structures, have been discussed. As explained above, the
AlH3). The decomposition of the less stable polymorph, g-
table indicates that there are considerable anomalies in the
AlH3, occurs by an exothermic transformation to the a phase
hydrogen storage capacities reported for carbon nanostruc-
(100 1C) followed by the decomposition of a-AlH3. However,
tured materials. The reported hydrogen uptake capacity
the reaction is not reversible due to the unfavorable
varies from 0.1 wt% to excess of 10 wt% [88–98]. The
thermodynamics. Ziden et al. and few others [76–78] have
capacity in excess of 10 wt% is not yet consistently repro-
suggested alternative techniques for the reproduction of
duced. However, there is room for developments as there
AlH3 through electrochemical routes. Very recently, Graetz
are theoretical studies predicting that high storage capacity
et al. [79] have shown a three step alane regeneration
in carbon nanomaterials is indeed possible [99]. One
pathway using dimethyethylameine (DMEA) which basically
another carbon nanostructure which is essentially quite
starts from the spent Al. The pictorial representation of the
different from the carbon nanostructures indicated in
formation of AlH3 is shown in Figure 5. In the first step,
Table 4 is carbon aerogels (CA) [100]. Recently Kabbour
alane amine (AlH3–C4H11N) complex was formed from the
et al. [101] have shown that the carbon aerogels can also be
catalyzed Al and DMEA under hydrogen environment. A
employed for hydrogen storage. Figure 6 shows the achieved
careful trans-amination was carried out in the second step
hydrogen storage capacity of various CA samples with
and the process was followed by the adduct separation for
different pore surface area, at 77 K within a pressure range
the clean separation of AlH3. AlH3 bearing composite
of 1–40 atm. Clearly, the hydrogen storage capacity
materials have also been investigated by few researchers.
enhances as the surface area of CA enhances, and the
In a recent study, Dulya et al. [80] have studied the
storage capacity of 5 wt% could be achieved in CAs
influence of mechanical treatment on decomposition tem-
possessing the pore surface area above 3000 m2/g. A major
perature of aluminum hydride when it is admixed with LiH,
fraction of this capacity gets stored under 1 to few bars.
MgH2, TiH2, VHx, and LiNH2. It was shown that the additives
Yet another interesting property of CAs is that they can
of LiH, MgH2, TiH2, and LiNH2 reduce the thermal stability of
act as nanoscaffold materials as well as good catalysts
AlH3.
[102]. CAs can be attached with catalysts such as TiCl3
and such functionalized CAs exhibit superior catalytic
Large surface area materials characteristics for hydrogen storage applications [102]. As
per the present trends, carbon nanostructures are not as
Carbon nanostructures supreme as complex hydrides/intermetallic hydrides for
Carbon nanostructures (CNS) are also widely investigated reversible hydrogen storage. However, CNS play dramatic
materials for hydrogen storage. Their large surface area to role in energy storage/conversion devices through their
volume ratio [81] offers large contact surface area/inter- excellent performances in electrochemical devices
face for the reaction with hydrogen gas. Maddox et al. [82] [103,104].
evaluated the adsorption of gases in materials with cylind-
rical pores (like tubes) by Monte-Carlo simulations in a
Grand Canonical Ensemble. In 1997, Dillon et al. [83] Metal organic frameworks
demonstrated hydrogen adsorption in carbon nanotubes by Metal organic frameworks (MOFs) are crystalline solids
temperature programmed desorption (TPD) method. Darkrim consisting of multidentate organic legends connecting metal
and Levesque [84,85] were the first to compute hydrogen ions or small metal containing clusters. MOFs have a three
adsorption in open end carbon nanotubes in a wide range of dimensional framework that encloses uniform pores which
High capacity hydrogen storage 573

Table 4 Hydrogen storage capacity of few carbon nanostructured materials and the details of experimental parameters.

Carbon variant H2 Capacity Pre-treatment Temp. Pressure Reference

(wt%) (1C) (atm)

SWCNT 1.7 HF washing & heating under Ar atm 196 1 [88]

MWCNT 1.12 9001C heating under Ar atm 196 100 [89]
Fullerenes 3.9 Controlled oxidation at 400 1C at 2 bar O2 196 120 [90]
atm
Activated carbon 1 Degassing at 400 1C for 48 h 20 100 [91]
Graphite 1.4 Decorate with Ti and sonicated for 16 h 30 1 [92]
Graphitic o1 Temperature treatment at 600 1C 20 30 [93]
nanofibres
Graphene 0.4 1 atm pressure swing at cryo-temperature 196 1 [94]

Figure 6 Hydrogen storage capacity of carbon aerogels. The

storage capacity varies depending upon the pore size of the
aerogel. Note that carbon aerogels can also be used as powerful Figure 7 The surface area dependence of MOFs with the
nanoscaffold material. Reproduced with permission from hydrogen uptake at 77 K under low and moderate pressure
Ref. [101], Copyright& (2006) American Chemical Society. hydrogen. Reproduced with permission from Ref. [111], Copy-
are interconnected forming an ordered network of chan- right& (2012) American Chemical Society.
nels. They are synthesized by a self-assembly process [105]
in which different combinations of organic linkers and metal hydrogen. It is due to the fact that, all the available surfaces
nodules lead to materials having a wide range of varying cannot be fully covered by H2 molecules at lower pressures.
topologies and pore size. After removal of retained (solvent) Also, it is now believed that, hydrogen adsorption in MOFs
molecules, a common as-grown MOFs show a very large under lower pressures is influenced by factors such as, pore
surface area; values in the range of 1500–3000 m2/g size, catendation, ligand functionalization, the availability of
[106–108]. Roswell et al. [109] have reported a MOFs system open metal sites, etc. [112]. For understanding the wide
having surface area greater than 5000 m2/g. It is reported number of MOFs considered for drawing such considerations,
by Chen et al. [110] that, since MOFs have an interpene- the reader is referred to the recent review of Suh et al. [111]
trated dynamic framework with high porosity, hydrogen can and the references cited therein. It is now known that there
be adsorbed under affordable operating conditions. Since are ways through which hydrogen storage capacity of MOFs
the metal atom attached surfaces possess higher catalytic can be improved under lower pressures. The few recent
activity, the system gets catalyzed and desorbs hydrogen approaches are (i) synthesizing MOF with narrow pores (best
under lower temperatures. in the subnanometre range), (ii) increasing the interaction
Recently, Suh et al. [111] have demonstrated an interesting energy between the porous solid and adsorbed hydrogen
relationship between the surface area of many MOFs and the molecules by applying catalysts, etc. Attention is also being
hydrogen uptake capacity. They have shown that storage of paid to increase the rigidity of the framework by using
even 10 wt% is possible at moderate pressures (in the range of electron donating substituents. The ab-initio (MP2) calcula-
10–90 atm) using MOF having surface area in excess of tions performed by Hubner et al. [112] revealed that the
6000 m2/g. However, at lower pressures (around 1–2 atm), interaction energy of MOFs with the hydrogen molecule is only
the MOFs does not offer any considerable hydrogen absorption marginally enhanced by electron-donating substituents. A
capacity. One can see this in Figure 7 that MOFs with surface more viable approach seems to be to focus on metal centers,
area even in excess of 2000 m2/g do not seem to absorb much particularly for MOFs having short linkers. Increasing the
574 D. Pukazhselvan et al.

polarizing ability of metal centers may significantly enhance

Table 5 List of few commonly known complex
interaction energy, as found for zeolites. This strategy was
borohydrides.
followed by Long and Dinca [113] and the hydrogen adsorption
heat was increased up to 9.5–10.1 kJ/mol H2 in some MOFs Complex Hydrogen Desorption Reference
with surface exposed Mg2 + or Mn2 + metal centers, which hydride capacity temperature
constitutes a significant step in the desired direction. In spite (wt%) (1C)
of all these developments MOFs are not yet considered as
preferred materials for applications due to insufficient rever- Li[BH4] 18.4 380 [117–120]
sible hydrogen storage behavior under mild operating condi- Na[BH4] 10.6 565 [121]
tions and also due to their poor micro-structural stability. K[BH4] 7.4 584 [122]
Be[BH4]2 20.7 123 [123]
Mg[BH4]2 14.8 320 [124]
Light weight complex metal hydrides
Ca[BH4]2 11.47 367 [125–126]
Al[BH4]3 16.8 44.5 [117,118]
Complex hydrides are interesting candidates for hydrogen Ti(BH4)3 13 70–90 [127,128]
storage due to their high hydrogen capacity (5–20 wt%) both
Zr(BH4)4 10.6 30 [129,130]
volumetrically as well as gravimetrically. (e.g., KAlH4:
5.5 wt%, LiBH4: 18 wt%). In contrast to the interstitial
hydrides, where hydrogen sits on and comes out of inter-
stitial sites without affecting the lattice of the host, The results indicated that the bond between (M + )n cations
desorption of hydrogen from complex hydrides lead to and [BH4] anions in M[BH4]n is ionic and the charge transfer
complete decomposition of the complex hydride phase. to [BH4] anions from (M + )n cations is responsible for the
Two types of complex hydrides which are investigated in stability of M[BH4]n. The general decomposition reaction of
detail for hydrogen storage are complex boron hydrides and alkali metal tetrahydroborates is described by the following
complex aluminum hydrides. Upon decomposition, complex equation:
hydrides liberate hydrogen through more than two steps and ABH4 -ABH2 þH2 -AH þB þ3=2H2
form binary hydride phase. Therefore, part of the storage
capacity is usually retained in form of stable binary light ðA : alkali metalsÞ ð10Þ
metal hydrides. A continuously updated list of complex For alkaline earth metal tetrahydroborates the decom-
hydrides can be found in the hydride database of Sandia position reaction is described by the following equation:
National Laboratory [114]. The survey shows, the most
promising class of materials at present is the alanate- and EðBH4 Þ2 -EH2 þ 2B þ3H2
borate-based complex hydrides. Although many complex ðE : alkaline earth metalsÞ ð11Þ
hydrides are presently known, many of them are so far only
ill characterized and the thermo-chemistry is not known The physical properties of the tetrahydroborates are, still
clearly. The following discussion therefore primarily focuses to a large extent, not known. As per the known thermo-
on those materials which have been reasonably well char- dynamic data, they are less promising candidates than
acterized and show promise for reversible hydrogen storage aluminohydrides for hydrogen storage due to the unfavor-
for mobile and stationary applications. able thermodynamic properties for reversible hydrogen
storage. However, with their higher capacity of hydrogen
than aluminohydrides, they are at present considered
Complex boron hydrides interesting candidates for hydrogen production through
Boron is known to form unstable polymeric hydrides (e.g. their reaction with water. An in-depth review of different
(BH3)x) [115]. The monomer BH3 is a strong lewis acid which types of complex borohydrides can be seen in the report of
achieves electronic saturation by dimerization [diborane Enis et al. [134].
(B2H6)]. Boron can also make complex hydride [BH4]
through additional charge localization in boron atom. The
H atoms are located at the corners of the tetrahedral [BH4] Complex aluminum hydrides
where boron coordinates the hydrogen atoms locating at the Reaction of hydrogen with aluminum lead to the formation
center. Localization of additional charge for the stabiliza- of the covalently bonded binary hydride phase called alane
tion of the complex boron–hydrogen tetrahedron is usually (AlH3). As in the case of complex borohydrides, the 18
achieved by charge transfer from alkali or alkaline earth or electron octet configuration can be achieved by localizing
by few transition metals [116]. Some of the boron complex one more electron and a hydrogen atom in alane. Electro-
hydrides and the corresponding hydrogen capacity are listed positive elements like Na, K, Li, Mg, and Ca can be used to
in Table 5. localize the additional charge in Al which lead to the
Nakamori et al. [131] have found a correlation between the formation of [AlH4] complex. Therefore due to the transfer
electronegativity of the cation and the frequency of the of electron(s), there is ionic bonding between M (alkali or
bending and stretching modes of hydrogen in the anion as alkaline earth metal) and AlH4 [135]. Some of the most
well as the melting temperature of the complex hydride. common complex aluminum hydrides are listed in Table 6.
Frankcombe et al. and Ohba et al. [132,133] have system- The storage capacity of LiAlH4 is 10.5 wt%. However,
atically investigated the thermodynamic stabilities for a series LiAlH4 has not yet been considered as a hydride of choice
of metal tetrahydroborates M[BH4]n (M=Li, Na, K, Cu, Mg, Zn, for commercial applications because of the irreversible
Sc, Zr and Hf; n=1–4) by first-principles calculations. dehydrogenation reactions. Synthesis of LiAlH4 was achieved
High capacity hydrogen storage 575

Table 6 The commonly known complex aluminum hydrides. The mixed cation complex aluminum hydrides are also given in
the table.

Complex Hydrogen Desorption Desorption Status of Reference

hydride capacity temperature (1C) enthalpy reversibility
(wt%) (kJ/mol H2)

Step 1 Step 2 Step 1 Step 2

LiAlH4 10.5 150 (5.3 wt%) 180 (2.6 wt%) 10 25 Not reversible [136]
NaAlH4 7.4 185 (3.7 wt%) 230 37 47 Reversible (5.5 wt%) [36]
(1.85 wt%)
KAlH4 5.7 290 (2.9 wt%) 350 (1.4 wt%) 55 70 Reversible (4.2 wt%) [137,138]
Mg(AlH4)2 9.3 140 (6.9 wt%) 280 (3.6 wt%) 41 76 Not reversible [139]
Ca(AlH4)2 7.8 127 (1.0 wt%) 250 (4.2 wt%) 7 28 Not reversible [140]
LiMg(AlH4)3 9.7 100 (4.8 wt%) 100 (2.8 wt%) 15.1 – Not reversible [141–143]
Na2LiAlH6 6.98 245 – 53.571.2 – Reversible (2.6 wt%) [144,145]
K2NaAlH6 4.47 325 – 98 – Reversible [146]
K2LiAlH6 5 227 – 82 – Reversible (2.5 wt%) [147]
NaAlH4 +Mg(AlH4)2 7.5 140 – – – – [148]
mixture

for the first time in 1947 by Finholt et al. [149] following the studies have been performed for understanding the feasi-
chemical reaction: bility of reversible hydrogen storage in LiAlH4. The recent,
systematic empirical thermodynamic calculation using
4LiH +AlCl3-LiAlH4 +3LiCl (12)
existing experimental data performed by Jang et al. [155]
revealed that more than 103 bar of hydrogen pressure is
But this is not an effective synthesis process because three
necessary to induce the hydrogen absorption reaction of
fourth of the lithium gets wasted in LiCl while only one fourth
Li3AlH62LiAlH4 above room temperature. Therefore it is
of the lithium is used in the formation of LiAlH4. Later, Ashby
not possible for a reversible reaction between Li3AlH6 and
et al. and Clasen [150,151] have proposed a solvent mediated
LiAlH4 to occur under practical conditions. LiAlH4 has been
method for the formation of LiAlH4 using diethyl ether,
extensively investigated by introducing many catalysts such
tetrahydrofuran and diglyme solution. While Clasen used
as TiO2 [156] and carbon nanoforms [157]. However, rever-
low pressure (30 bar) and low temperature (308 K) condi-
sible hydrogen storage in LiAlH4 remains a challenging task.
tions, Ashby et al. carried out the synthesis with 350 bar
Recently the team of McGrady and Jensen [158,159] have
pressure of hydrogen at 393 K. Recently Wang et al. [152]
shown the possibility of reversible hydrogenation in Li–Al–H
proposed a five-step physiochemical pathway for the produc-
system. They have made an activated mixture of LiH and Al
tion of crystalline LiAlH4 from Li3AlH6, LiH and Al. A direct
using TiCl3 catalyst and then the hydrogenation of the
synthesis of LiAlH4 from LiH and Al by a mechanochemical
mixture was accelerated by Me2O solvent. The TPD diagram
reaction was done by Kojima et al. [153]. They proposed
as seen in Figure 8 shows the test runs of materials such as
milling for 24 h under 1 MPa hydrogen pressure at room
hydrogenated LiH/Al/TiCl3 (in the ratio of [Link].0001,
temperature, but the yield of LiAlH4 was very less. More
denoted as (a)), hydrogenated LiH/Al/TiCl3 (in the ratio of
recently, a low energy route to form LiAlH4 from LiH and Al
[Link].0005, denoted as (b)), hydrogenated LiH/Al/TiCl3 (in
was demonstrated by Graetz et al. [154]. The dehydrogena-
the ratio of [Link].002, denoted as (c)), hydrogenated LiH/
tion reaction of LiAlH4 proceeds in three steps as follows:
Al/TiCl3 (in the ratio of [Link].005, denoted as (d)), hydro-
3LiAlH4-Li3AlH6 +2Al+3H2 (13) genated LiH/Al/TiCl3 (in the ratio of [Link].01, denoted as
(e)), hydrogenated LiH/Al/TiCl3 (in the ratio of [Link].02,
denoted as (f)), etc. It is interesting to note that the
Li3AlH6-3LiH +Al + 32H2 (14) capacity in excess of 6 wt% is reversibly generated with
good desorption performances and the capacity is largely
LiH-Li + 12H2 (15) affected by the concentration of the TiCl3. The authors
found that long run reversibility is possible, but presently
The first step dehydrogenation occurs exothermically with the repeated runs do not seem to provide consistent
DH=10 kJ/mol H2 at 150–180 1C releasing 5.3 wt% of H2. capacity. It was also interesting to note that the result
The second reaction occurs endothermically with DH =25 was not achieved when catalysts such as metallic Ti, Nb2O5
kJ/mol H2 at 180–220 1C with the release of 2.6 wt% of H2. and NbCl5 were employed. It should be noted that the
The third reaction occurs only at higher temperatures above understanding regarding the mechanism of catalyst is very
400 1C with an enthalpy of 140 kJ/mol H2. The hydrogen important in such areas. If the mechanism of catalyst is
desorption kinetics of LiAlH4 system is better than that of known clearly, then it could be easier to narrow down the
NaAlH4. However, the main reason for not using LiAlH4 for catalytic selectivity so as to engineer high capacity hydro-
practical applications is its irreversibility. A number of gen storage materials with suitable property. Lots of
576 D. Pukazhselvan et al.

very slow [173]. The dehydrogenated products combine

back to form NaAlH4 only above high pressure hydrogen
(4150 atm) at 200 1C. Due to these reasons, sodium alanate
was not considered a viable candidate for reversible hydro-
gen storage until the report of Bogdanovic et al. in 1997.
The total hydrogen capacity of NaAlH4 is 7.4 wt% and
hydrogen liberation occurs by the following reactions [174]:
3NaAlH4-Na3AlH6 +2Al+3H2 (3.75 wt% at 170–230 1C) (18)

Na3AlH6-3NaH + Al+ 32H2 (1.85 wt% at 230–260 1C) (19)

3NaH-3Na + 32H2 (1.8 wt% 4400 1C) (20)

Figure 8 Reversible hydrogen uptake kinetics of LiAlH4 The first and second step reactions together takes more
synthesized through high pressure milling using TiCl3 catalyst- than 50 h for the liberation of 5 wt% hydrogen (at tem-
accelerated by Me2O solvent. The LiH and Al concentration was peratures less than its melting point 183 1C [37]. The third
fixed at 1:1 ratio and TiCl3 concentration was varied for all step reaction is usually not considered because the deso-
the samples. The catalyst concentrations with LiH/Al mixture rption temperature 400 1C is too high from the operating
were as follows: (a) 0.00001 mol ratio, (b) 0.0005 mol ratio, conditions of IC engines or fuel cells (FC). Moreover the
(c) 0.002 mol ratio, (d) 0.005 mol ratio, (e) 0.01 mol ratio and reverse reaction (reversibility) is possible only under severe
(f) 0.02 mol ratio. Reproduced with permission from Ref. [159], reaction conditions. Bogdanovic et al. have used a variety of
Copyright& (2011) American Chemical Society. metal catalysts such as Ti, Zr, Fe, Mn etc. and observed that
Ti is the most effective catalyst. Many researchers have
investigated the desorption behavior of NaAlH4 using differ-
modeling and experimental efforts are being devoted to ent catalysts, however still the system performance deviates
understand the mechanism of catalysts in the case of much from the actual thermodynamic data. The PCT mea-
complex hydrides [160–165]. surements carried out on the pristine sodium alanate for
Sodium alanates (tetrahydroaluminate–NaAlH4 and triso- dehydrogenation in the temperature range of liquid
dium hexahydroaluminate–Na3AlH6) are known for decades as NaAlH4 resulted in the reaction enthalpy of 6.4 kJ/mol H2
reducing agents in synthetic chemistry. The solution mediated for first step desorption and 32.1 kJ/mol H2 for the second
synthesis method which was known for the preparation of dissociation step [173]. However, the re-examination of
LiAlH4 (1947) was followed again for the synthesis of NaAlH4 by these values through the PCT isotherms performed by
Finholt et al. in 1955 [166] and Kabbour et al. in 2007 [140]. Bogdanovic et al. provided 18.5 kJ/mol H2 and 15.7 kJ/mol
Na3AlH6 was synthesized for about 15 years later by Zakharin H2. These values indicate that NaAlH4 is indeed falling across
and Gavrilenko. [167]. Since then many attempts have been the thermodynamic window. Figure 9 represents a general
made for the synthesis of NaAlH4 which includes solvent view of the operation of NaAlH4–Na3AlH6–NaH system. The
mediated techniques [168], mechanical milling [169,170], two curves shown in Figure 9 divides the P–T map into three
and solvent free one step direct synthesis [171,172] in (or more precisely, four) parts. The shaded (dark) area (A)
presence of catalysts, etc. Ashby et al. have reported that represents solid phase and parallel lined area (B) indicates
the synthesis of NaAlH4 can be achieved by the following liquid phase region of NaAlH4. In the shaded area as indicated
equations: by A, NaAIH4 is thermodynamically stable. Around 183 1C and
135 atm, NaAlH4 gets liquefied. Na3AlH6 is stable inside the
Na+Al +2H2-NaAlH4 (16)
region of (C) (light shaded). The blank area (D) represents
the region of NaH/Al mixtures under hydrogen atmosphere.
NaH+ Al + 32H2-NaAlH4 (17) As per these data, the desorption of hydrogen at 1 atm
equilibrium pressure should be achieved under temperatures
The reaction was performed under tetrahydrofuran (THF) at 35 1C in the case of NaAlH4 (and at 110 1C in the case of
at 140–160 1C with hydrogen pressure of 140–350 atm. They Na3AlH6). As per the view point of Bogdanovic et al. [36], the
have used activated aluminum, the activation of the most effective catalyst for NaAlH4 is the one which offers the
aluminum was achieved by treating it in powder form with desorption closer to the temperature of 35 1C as indicated
triethylaluminum. The method described by Ashby et al. by the basic thermodynamic data of sodium alanates. Until
offers direct synthesis of NaAlH4 from elements Na and Al. then, the research opportunities through nanocatalysis are
However, since the employed pressure is very high this open for sodium alanate system.
process does not solve the question regarding the effective Recently, Balde et al. [175] have proved that the hydrogen
means of synthesis of NaAlH4. The synthesis methods for storage performances of NaAlH4 system is particle size depen-
NaAlH4 seem to be almost mature presently. For the state of dent. The team made it clear that the desorption temperature
the art synthesis methods of NaAlH4, the reader is referred of nano NaAlH4 occurs rapidly at temperatures 50 1C. As
to the works in Refs. [169–172]. shown in Figure 10a and b, the hydrogen desorption of NaAlH4
The pristine NaAlH4 releases hydrogen above its melting with sizes in the range 2–10 nm occurs almost exclusively at
point (183 1C, Dymova et al.) and the desorption kinetics is temperatures less than 100 1C, whereas in the case of NaAlH4
High capacity hydrogen storage 577

Figure 9 The P–T map of NaAlH4 system. The P–T map shows
that the reaction temperature of first and second step deso-
rption under normal pressure is 30 1C and 110 1C. Reproduced
with permission from Ref. [172], Copyright& (2000) Elsevier.

with sizes of 1–10 m, the hydrogen desorption occurs above

100 1C and goes beyond 200 1C. The activation energies of
NaAlH4 with sizes of 1– 10 nm, 19–30 nm and 1–10 m was
observed to be 58 kJ/mol, 79 kJ/mol and 116 kJ/mol,
respectively. Thus the work presents a classic illustration that
there are lot of scopes still in this system and reaching the Figure 10 (a) Temperature programmed desorption of NaAlH4
conditions as suggested by the thermodynamic factors (see the exclusively confined under nanopores of graphitic nanofibres
P–T map shown in Figure 9) is indeed possible. synthesized using SiO2 porous templates, (b) variation of
The hydrogen storage capacity of potassium alanate activation energy with respect to the size of NaAlH4 particles.
(KAlH4) is 5.7 wt%. Potassium alanate is a reversible hydride Reproduced with permission from Ref. [175], Copyright& (2008)
even in absence of catalysts. However limited works have so American Chemical Society.
far been carried out on KAlH4. This is due to the fact that
KAlH4 is not commercially available. Potassium alanate was
synthesized for the first time by Ashby et al. [168] by direct enthalpies of decomposition for the first two steps are
synthesis in toluene, tetrahydrofuran, and diglyme. Morioka determined as 55 kJ/mol H2 and 70 kJ/mol H2 [176]. Ares
et al. [137] have synthesized KAlH4 powder directly by heat et al. [138] have observed that TiCl3 catalyst reduces the
treatment of the KH and Al mixture at 270 1C under high first step desorption temperature of KAlH4 from 300 1C to
pressure of hydrogen (4175 bar). The enthalpies of forma- 250 1C but no significant temperature reduction took place
tion of KAlH4 and K3AlH6 were found to be 70 and in the second step reaction. For these thermodynamic
78.5 kJ/mol H2, respectively [176]. The dehydrogenation limitations and also the first two step reactions altogether
reaction of KAlH4 goes through the three step general possess only 4.3 wt%, KAlH4 is not paid extensive considera-
decomposition reaction as follows: tion as a practical storage candidate. However, KAlH4 is
useful for the synthesis of mixed complex hydrides (see
3KAlH4-K3AlH6 +2Al+ 3H2 (21) Table 6) which show enhanced thermodynamic character-
istics for high capacity reversible hydrogen storage [177].
Magnesium alanate is another high capacity complex
K3AlH6-3KH+ Al+ 32H2 (22)
hydride which received much attention for onboard hydro-
gen storage applications [178,179]. In the general formula
KH-K +½H2 (23) of MAlH4 (where M =Li, Na and K), when divalent alkaline
earth metal atoms are used in place of the monovalent
The first dehydrogenation occurs at 300 1C with the alkali metal atoms, two units of AlH4 can be attached with
release of 2.9 wt% hydrogen. The second step reaction the metal atom, [AlH4–M–AlH4]. Therefore, the high H/M
releases further 1.4 wt% hydrogen at about 340 1C and the ratio together with the light weight of M and Al makes the
third step reaction releases 1.4 wt% hydrogen at 430 1C. The gravimetric hydrogen capacity higher than the alkali metal
578 D. Pukazhselvan et al.

alanates. The hydrogen capacity of Mg(AlH4)2 is 9.3 wt%. can be hydrogenated to form Mg(AlH4)2 at standard pressure
Unlike NaAlH4 or LiAlH4, magnesium alanate is not commer- and 100 1C. However, this success does not seem to warrant
cially available mainly due to the lack of synthesis techni- a bulk scale reproduction of Mg(AlH4)2 so far and any further
ques affordable for bulk scale synthesis of pure Mg(AlH4)2. developments in this area remain to be seen. Recently Liu
Mg(AlH4)2 was synthesized for the first time by Wiberg and et al. [186] have shown that Mg(AlH4) +LiBH4 mixture
Bauer [180–182] through a solvent (diethyl ether) mediated possesses interesting synergetic characteristics and dehy-
technique: drogenation occurs even at temperatures 100 1C. Several
studies have been done so far to increase the desorption
4MgH2 +2AlCl3-Mg(AlH4)2 +3MgCl2 (24)
kinetics of Mg(AlH4)2 and to achive reversibility [187–190],
but the rehydrogenation trials are not yet successful due to
MgH2 +2AlH3-Mg(AlH4)2 (25) thermodynamic reasons.
The hydrogen storage capacity of calcium alanate is 7.8 wt%.
Ca(AlH4)2 was first synthesized by Schwab and Wintersberger
2LiAlH4 +MgBr2-Mg(AlH4)2 +2LiBr (26) [191] by the following route using THF solvent:
Ashby et al. and Claudy et al. [183,184] have used a 4CaH2 +2AlCl3-Ca(AlH4)2 +3CaCl2 (30)
solvent mediated approach to synthesis Mg(AlH4)2 which
includes a monovalent alkali metal alanate with divalent The purified and dried product contained 40% calcium
alkaline earth metal halide salts. The metathesis reaction tetrahydroaluminate, the rest being THF. Recently, synthesis
under tetrahydrofuran solvent results in Mg(AlH4)2 of calcium alanate has been achieved by a number of
advanced methods such as mechanical synthesis, wet che-
2MAlH4 +MgX2-Mg(AlH4)2 +2MX (27) mical synthesis, mechanically assisted wet chemical synth-
esis, etc. [192]. The decomposition reaction of calcium
The similar synthesis approach was employed by Fichtner and
alanate proceeds as follows:
Fuhr also [178]. One of the important things related to the
synthesis of Mg(AlH4)2 is the purity of the as-synthesized Ca(AlH4)2-CaAlH5 + Al+ 32H2 (31)
material. The above described methods provide alkali halide
salt by-products as dead weight so the effective hydrogen
capacity gets affected. Fichtner et al. have separated Mg(AlH4)2 CaAlH5-CaH2 +Al+ 32H2 (32)
using Soxhlet extraction technique. It was reported that the
extraction approach provides nearly 80% pure Mg(AlH4)2. CaH2-Ca + H2 (33)
Recently Mamatha et al. and Hudson et al. [143,148] have used
another method for the synthesis of NaAlH4 called mechano- The enthalpy of the first step dehydrogenation reaction is
chemically activated matathesis reaction. The reactants NaAlH4 estimated to be 7 kJ/mol H2 which shows the metastable
and MgCl2 were taken in a 2:1 ratio and milled under inert nature of Ca(AlH4)2 [193], while the enthalpy difference for
atmosphere using a mechanical miller. The metathesis reaction
dehydrogenation of CaAlH5 is found to be 28 kJ/mol H2 at
has been found to be mechanically activated and the reaction
was completed within 1 h. Hudson et al. have purified the ambient conditions [194]. The third step occurs at much
reaction products using Soxhlet extraction method as suggested higher temperature with an endothermic enthalpy of
by Fichtner et al. and separated 30% of the NaCl. The + 172 kJ/mol H2. These results are in agreement with those
difference in the amount of NaCl separation achieved by previously reported by Mamatha et al. [141,143] who
Fichtner et al. and Hudson et al. may be due to the differences studied the dehydrogenation characteristics of calcium
in the number of Soxhlet extraction runs made by these alanate and observed that the first reaction occurs at
investigators. 127 1C (exothermic reaction) and the second reaction occurs
The thermal dehydrogenation reaction of Mg(AlH4)2 does at 250 1C (endothermic). Thus these values suggest that
not follow the general dehydrogenation reaction of alkali
calcium alanate possesses closer thermodynamic features
metal alanates where the desorption goes through hexahy-
with the targeted values for onboard hydrogen storage
droaluminate phase. The irreversible dehydrogenation reac-
tion of Mg(AlH4)2 proceeds through a two step reaction path applications. However, as per the view point of Iosub
as follows: et al., since the decomposition of Ca(AlH4)2 is more complex
than other previous reports in literature, a thorough
Mg(AlH4)2-MgH2 +2Al +3H2 (28)
thermodynamic assessment is required for this system [195].
In addition to the alkali–alkaline earth metal alanates,
2Al+MgH2-12Al3Mg2 + 12Al+H2 (29) another set of hydrides which fall in the category of
complex aluminum hydrides is alanates with different
The first step occurs at 140 1C with the release of cations. As for example, lithium magnesium alanate, sodium
6.9 wt% H2, and the remaining hydrogen gets liberated at lithium alanate, lithium potassium alanate, etc. Since, the
340 1C with the formation of intermetallic compound alkali or alkaline earth alanates discussed above exhibit
Al3Mg2. Fichter et al. have also shown that the desorption some shortcomings in kinetics and thermodynamics,
kinetics of Mg(AlH4)2 can be significantly improved by Ti research attention is focused on mixing cations with slightly
catalyst but there were no traces for the restoration of different electronic characteristics so as to achieve prop-
Mg(AlH4)2 under the studied conditions. Gremaud et al. erty tuned alanate system. Some commonly known mixed
[185] have shown that, Mg–Al thin films capped by Pd layers cation alanate system is summarized in Table 6. More
High capacity hydrogen storage 579

informations are available on these works [142–148] and the

Reference
references cited therein.

[197]
[198]
[199]

[200]
[201]
[202]
Other hydrogen storage materials

Amide/imide system
Alkali-metal amides are known as reagents in synthetic
Reversibility

organic chemistry. The synthesis of few metal amides and

their basic reactions related with hydrogen were reported by
Bergstrom and Fernelius in 1993 [196]. Recently, it has been
(wt%)

demonstrated that amide/imide system reversibly stores

5.5

1.1

5.4
2.5
hydrogen under moderate reaction temperatures. The work
–

–
of Chen et al. [197] on lithium amide system motivated
extensive studies and subsequently a series of amide/imide
temp (1C)

system has been investigated by various researchers

Dehyd.

[198–205]. A brief summary of some widely investigated

amide/imide system is given in Table 7.
280
200
350

200
350
150

Chen et al. have reported that 10.4 wt% hydrogen can

be reversibly stored by the following reaction path in Li–N–H
system:
Dehyd. enthalpy

Li3N +2H22Li2NH+LiH +H22LiNH2 +2LiH (34)

(kJ/mol H2)

The reaction kinetics was slow and the temperature

required for dehydrogenation is also much higher (see
Table 7). Ichikawa et al. [206] have shown that kinetics
44.1
3.5
99

can be improved by TiCl3 catalyst. Orimo et al. and

–

–
–

Nakamori and Orimo [207,208] have shown that the hydro-

gen storage characteristics of the above system can be
enhanced by employing Li with Mg partially. Thus, a mixture
observed/actual (wt%)

of Li3N and Mg3N2 has been made which yielded 9 wt%

hydrogen through the following reaction:
3Mg(NH2)2 +12LiH2Mg3N2 + 4Li3N +12H2 (35)
H2 Capacity
Few commonly known amide/imide system for hydrogen storage.

This trail resulted in dramatic improvement in the desorption

kinetics under comparatively lower temperatures without much
0.90
0.95
0.95

0.96

0.99

reduction in the hydrogen capacity. Lohstroh and Fichtner [209]

1.0

have investigated Mg–Li–N–H system and shown that TiCl3 is an

effective catalyst for 2LiNH2 +MgH2. However, the catalyst got
poisoned within two hydrogenation cycles. Many catalysts such
as Mn and V [210], carbon nanostructures (SWCNT, MWCNT and
Mg(NH2)2 + 2LiH)-Li2Mg(NH)2 + 2H2
Ca(NH2)2 + 2LiH-CaNH +Li2NH+ 2H2

activated carbon) [211] were investigated for the past couple of

Mg(NH2)2 + 2MgH2-Mg3N2 + 4H2

years. Ichikawa et al. [212] have proposed that the hydrogen

Ca(NH2)2 + CaH2-2CaNH + 2H2

desorption reaction of (34) actually proceeds through the

2CaNH+ CaH2-Ca3N2 + 2H2

following two-step elementary reaction mediated by ammonia:

2Al+ Li2NH+ LiH + 4H2

2LiNH2-Li2NH +NH3 and LiH +NH3-LiNH2 +H2 (36)

LiNH2-Li3N + 2H2

LiNH2 + 2LiAlH4-
Reaction route

Yao et al. observed that the catalyst enhances the release of

NH3 from LiNH2, but show only little influence on the produc-
tion of H2 from the LiNH2 +LiH mixture. From these results, it
was concluded that the rate-limiting step for dehydrogenation
from the mixture was the reaction between LiH and NH3. For
the application of the metal–N–H system in hydrogen storage
technologies, ammonia release should be avoided or minimized.
MgNH2/Mg3N2
Amide/imide

Amino boranes
LiNH2/Li3N

Ammonia-Borane (AB), H3NBH3, in recent times is an intri-

Li–Mg–N–H
Ca(NH2)2/

Li–Ca–N–H
Li–Al–N–H
Table 7

guing candidate for hydrogen storage applications. Due to

Ca3N2

the high gravimetric hydrogen density (19.6 wt%), and

appreciable enthalpy (–21 kJ/mol H2) H3NBH3 has been
considered as an attractive candidate [213,214]. However,
580 D. Pukazhselvan et al.

devising an energy-efficient chemical process to regenerate Clathrates and zeolites

H3NBH3 from dehydrogenated B–N–Hx system is an important Besides chemisorption and physisorption process, a third way
step for hydrogen storage applications. The first report on of storing hydrogen is encapsulation of the gas inside a guest
synthesis of NH3BH3 was made in 1955 by Shore and Parry [215]. (solid) structure to form a clathrate from which hydrogen can
They have synthesized AB by reacting LiBH4 either with NH4Cl be released by a pressure and temperature swing [220]. A
or (NH4)2SO4 under diethyl ether medium. A brief description clathrate or cage compound is a chemical substance consist-
about the number of advanced synthesis methods for AB can be ing of a lattice of one type molecule trapping and containing
obtained from the detailed review of Staubitz et al. [216]. In a second type of molecule (e.g., methane clathrates, also
order to release hydrogen from AB one has to either thermally called methane hydrates, methane molecules trapped inside
decompose this (thermolysis) or react it with water (hydrolysis). a ‘cage’ of ice crystals). It was in 1999 when the first report
In the process of thermolysis hydrogen gets liberated by three on hydrogen clathrate hydrates appeared, which prompted
steps which require temperatures of 100 1C, 150 1C and 500 1C. extensive research on other hydrogen clathrates as potential
The desorption reactions can be written as follows: materials for hydrogen storage.
Dyadin et al. [221] studied the H2O:H2 system by differ-
NH3BH3-(NH2BH2)n(s) +nH2(g) (37)
ential thermal analysis and found a temperature region
exhibiting anomalous melting behavior and kinetics of ice
(NH2BH2)n(s)-(NHBH)n(s)+ nH2(g) (38) melting at hydrogen pressures of 100–360 MPa. They hypothe-
sized that a clathrate phase of hydrogen hydrate was formed
in this pressure range. Following that work, the clathrate
NHBH(s)-(BN)n(s) +nH2(g) (39) phase sII (sII is the type II cubic cage structural phase of
clathrates; more relevant information can be obtained from
By catalyzed hydrolysis reactions of AB, storage capacity of [Link]
7 wt% with faster reaction kinetics can be achieved. However, [Link]) of hydrogen hydrate was synthesized by Mao
by these routes also, no straight reversible pathways are et al. from a liquid at a pressure of about 200 MPa and at
demonstrated. Recent studies have focused to reprocess the 24 1C. Mao et al. suggested that four hydrogen molecules are
reaction products so as to make use of spent chemicals stored in a large sII clathrate cage, and two hydrogen
obtained at the end of the reaction. Wolf et al. and Hausdorf molecules are stored in a smaller cage. Lee et al. [222] have
et al. have demonstrated the possibility of reversible genera- reported that hydrogen storage capacities in THF-containing
tion of AB through modified reverse reaction pathways binary-clathrate hydrates can be increased to 4 wt% at
[217,218]. However, the methods explained in the literatures modest pressures by tuning their composition to allow the
are tedious, so it is reasonable to assume that commercial hydrogen guests to enter both the larger and the smaller
viability of AB system is yet to be exposed. In one of the recent cages, while retaining low-pressure stability. The capture of
breakthroughs in AB system, Sutton et al. [219] have shown that H2 in H2O cages to give clathrate hydrogen hydrate is a
regeneration of AB is possible by off-board chemical treat- breakthrough in the development of hydrogen storage mate
ments. They have demonstrated that the hydrogen desorption rials. However, pure H2 hydrate is stabilized only under high
reaction of AB has to be carefully controlled to form polybor- pressures (typically 220 MPa at 249 K). Hu and Ruckenstein
azylene (PB). This PB can be converted back to AB by a 24-h [223] have shown that inclusion of THF as a second guest
hydrazine (N2H4) treatment under liquid ammonia (NH3) at allows stabilization of the resultant clathrate at pressures of
40 1C. The reaction product observed at the end consists of 8% only 5 MPa at 279.6 K and it can also store significant amount
hydrazineborane and 92% AB. The ideal chemical reaction as of hydrogen. As far as the present state of the art is
shown in (40) suggests that every 1 mol of PB requires 1.25 mol concerned, storage of hydrogen using clathrates is an area
of hydrazine for the regeneration of AB. which needs extensive investigation mainly to stabilize the
4BNH+ 5N2H4-4H3N–BH3 +5N2 (40) clathrates under affordable operating conditions.
Zeolites are porous aliminosilicate networks, usually accom-
The representative chemical reaction cycle for the formation modating wide variety of cations, such as Na + , K + , Ca2 + , Mg2 +
of AB from the dehydrogenated products is shown in Figure 11. and others [224,225]. The positive ions are rather loosely held
and can readily be exchanged in a contact solution. Zeolites
received interest as possible hydrogen storage candidates
[226] because the diameter of the cages and the channels
can be controlled by exploiting their ion-exchange property to
modify the valence state and the size of the exchangeable
cations. The work of Fraenkel [227] revealed that there can be
direct manipulation of the available void space of the zeolite
and the chemical nature of possible binding sites to ease the
access of hydrogen molecules to the internal pore space. The
study of Langmi et al. revealed that zeolites can store small
amounts of hydrogen (0.3 wt%). However, under cryogenic
Figure 11 Schematic of the reversible hydrogen pathway and conditions, substantially higher hydrogen storage capacities
the steps proposed by Sutton et al. [219] for the regenertion of (1 wt%) can be reached. Recently, researchers in Spain [228]
spent ammonia borane. Adapted with permission from Ref. have found that a zeolite-Y partially exchanged with magne-
[219], Copyright & (2011) The American Association for the sium cations (Mg2 + ) has an unprecedented high adsorption
Advancement of Science. enthalpy of 17.5 kJ/mol, which is closer to the USDOE’s
High capacity hydrogen storage 581

target. However, from the capacity point of view zeolites are study revealed that when a titanium atom is attached to a
not yet the candidates for hydrogen storage system to be used polyacetylene polymer the system shows promising hydro-
in devices. gen uptake under ambient temperatures and pressures.
However, this is not yet proved experimentally.
Glass microspheres and capillary arrays Recently, Senoz and Wool of Delaware [235,236] have
Akunets et al. [229] have shown that compressed hydrogen shown the possibility of storing hydrogen in a compound
can be safely stored in hollow glass microspheres. Hydrogen derived from chicken feather. The research report reveals
encapsulation is accomplished by heating a bed of empty that ‘‘keratine’’, a compound found in bird feathers (92%),
hollow glass microspheres in an atmosphere of hydrogen. absorbs hydrogen in appreciable amount. The keratine
Hydrogen permeates into the hollow cores of the micro- based chicken feathers have been initially carbonized by
spheres through the thin glass shells at practical rates at heat treatment with controlled pyrolysis, which results in
temperatures between 100 1C and 400 1C. Hydrogen within the formation of hollow carbon microtubules with nanopor-
the microspheres is trapped since the permeation rate is ous walls. Their specific surface area increases up to
drastically lower at room temperature. To extract the 450 m2/g by the formation of fractals and micropores. Thus
hydrogen from the microspheres, the filled microspheres the pores enable hydrogen adsorption of up to 1.45 wt%
are placed in a low pressure vessel and reheated to a lower under 40 atm pressure and 400 1C.
temperature than that required for filling. Unfortunately,
the inherently poor thermal conductivity of inorganic Liquid hydrides
glasses, enhanced by the morphology and size of the hollow Hydrogen can also be reversibly stored in unsaturated
microspheres, resulted in poor hydrogen release rates. hydrocarbons. The reaction takes place reversibly at mod-
Shelby et al. [230] have demonstrated that storage capacity erate temperatures with relatively high storage capacity.
of 6 wt% is possible under affordable conditions. It is Hodoshima et al. [237] have shown a high capacity system
suggested that the combination of high storage capacity with storage capacity of 7.3 wt% (decalin2naphthalene)
with rapid response provided by photoinduced hydrogen
diffusion in microspheres (containing selected dopants) C10H182C10H8 +5H2, (DH= 297.3 kJ/mol H2) (40)
offers good prospects for meeting the requirements for
applications. However, difficulties in producing the ideal Another system (heptane2toluene) with storage capa-
spherical shape of uniform diameter and wall thickness are city of 8 wt% was shown by Newson et al. [238].
drawbacks of glass microspheres. The eccentricity and C7H162C7H8 +4H2, (DH =252 kJ/mol H2) (41)
diameter spread often lead to the collapse of the spheres
under high external pressure during filling of the spheres Cyclohexane and methylcylohexane are the two other
with hydrogen. Similar to the hollow spheres, another widely studied liquid hydride systems for hydrogen storage.
system-capillary arrays have also been studied by Zhevago The reactions routes of cylohexane2benzene and methy-
and Glebov [231]. They are a bundle of cylinder capillaries lyclohexane2toluene offer 6 wt% reversible hydrogen
sealed at both ends with semi-spherical caps and packed in capacity [239,240].
a 2D hexagonal lattice. The recent report of Zhevago et al.
[232] reveals that more than 10 wt% hydrogen can be stored C6H122C6H6 +3H2, (DH =206 kJ/mol H2) (42)
in quartz cylinder capillaries (480 mm external diameter and
25 mm wall thickness). However, since pressure is required C7H142C7H8 +3H2, (DH =215.3 kJ/mol H2) (43)
in excess of 2000 atm for achieving this capacity, this seems
to be not a viable storage material presently. However, these reactions are not quite amenable towards
dehydrogenation under practically possible conditions for
Polymers
applications. As for example, the catalyzed reaction (43)
Microporous organic polymers were also found to offer the
takes place at temperatures above 400 1C, which also
possibility of storing hydrogen safely at low temperatures
results in the formation of undesired carbonaceous deposit
and moderate pressures by physisorption of hydrogen.
on the catalyst and poison the catalyst.
McKeown et al. [233] have studied a range of polymers of
intrinsic microporosity (PIMs). They have shown that a
polymer based on a triptycene monomer takes up 2.7 wt% New approaches in metal hydride research and
H2 at 10 bar/77 K. Hyper cross linked polymers (HCPs) were road ahead
also shown to possess promising performance, particularly
at pressures 410 bar. It was shown that the isotherm is In thermodynamic terms (i.e. apart from kinetics), in order
influenced by the micropore distribution of the polymer. to achieve a dissociation equilibrium pressure of 1–10 bar at
A higher concentration of ultramicropores (pore size 0–100 1C (i.e., suitable for many practical applications),
o0.7 nm) is associated with enhanced low pressure adsorp- the enthalpy of dissociation must be in the range of
tion. Very recently, Ihm and his group [234] at Seoul 15–24 kJ/mol H2 [241] (‘‘This is known as the thermody-
National University proposed a new polymer system with namic window for metal hydrides’’). Due to this thermo-
the hydrogen storage efficiency of 7.6 wt% gravimetric dynamic restriction, many of the metal hydrides with high
hydrogen density and 63 kg/m3 volumetric hydrogen density hydrogen capacity are not applicable for hydrogen storage
under ambient conditions. They performed first-principles because of their either too high or too low thermodynamic
electronic structure calculations for hydrogen binding to stability. For example, the reversible MgH2/Mg system
metal-decorated polymers of many different kinds. The (7.6 wt% H2) does not seem to be practicable for mobile
582 D. Pukazhselvan et al.

hydrogen storage purposes, since the dissociation pressure

of 1 bar is achieved only somewhat below 300 1C) [242].
Thorough analysis of the various kinds of hydrogen storage
materials reveal that it is largely unlikely that any of the
pristine hydrogen storage materials discussed in the pre-
vious sections will be suitable as hydrogen storage cylinders.
This is due to the fact that the required capacity range may
not be met under affordable operating conditions. However
new promising concepts of hydrogen storage are emerging
through which breakthroughs in future are foreseeable. As
for example, nanoscaffolding [243–245], reactive hydride
composites [246–250], new alkali–alkaline earth ternary
metal hydrides [251], etc.
Nanoconfinement of hydrides is a promising material
processing technique by which the hydrogen storage per-
formances of hydrides can be dramatically improved. As for
example, the model system NaAlH4 is known as a thermo-
dynamically feasible candidate for reversible hydrogen
storage even under room temperature. But, the bulk system
exhibits huge activation energy barrier and behaves entirely
different from what is suggested by the thermodynamics of
the material. Many other systems such as LiBH4, NH3BH3,
LiAlH4, MgH2 are also known to exhibit the similar trend
[252–255]. Top down approaches can be used for controlling
the size of particles, but during the repeated cycling runs,
smaller particles agglomerate together and the system
becomes bulk again. The better way to control the size is
by confining the hydrides inside the nanochannels of scaf-
fold materials, as for example, carbon aerogels, silica
aerogels, porous carbon fibers etc. Melt infiltration is a
promising new concept through which one can impregnate
high capacity hydrides inside the narrow nanochannels of
scaffold materials. One can notice the liquid phase region of
NaAlH4 in the P–T map shown in Figure 9. If we manage to
apply the conditions required for melting NaAlH4, as sug- Figure 12 (a) and (b) The TPD characteristics of nanoconfined
gested by P–T map, this melt can be shed and confined to sodium alanate system. The catalyst pre-functionalized with
the nanochannels. scaffold material offers superior result. (i) Ball milled pristine
An illustrative example of the effect of nanoscaffolding NaAlH4, (ii) 1 h ball milled NaAlH4 with TiCl3 catalyst, (iii) long
can be visualized in Figure 12a and b [113]. Figure 12b hours ball milled NaAlH4 with TiCl3 catalyst, (iv) infiltrated
compares the TPD characteristics of (i) ball milled NaAlH4 NaAlH4 in RF carbon aerogel, (v) infiltrated NaAlH4 in a RF
without catalyst, (ii) 1 h ball milled NaAlH4 with TiCl3 carbon aerogel attached with TiCl3 catalyst. Reproduced with
catalyst and (iii) long hours ball milled NaAlH4 with TiCl3 permission from Ref. [102], Copyright & (2011) American
catalyst., As seen, the ball milled samples offered better Chemical Society.
performances, but no significant temperature reduction is
achieved by the long or short time ball milling. However, much attention. This reactive hydride composite system
when neat NaAlH4 is allowed to infiltrate in the 17 nm pores is interesting in the sense that they react with each
of RF aerogels (see Figure 12a (iv)) the desorption starts at other under moderate operating conditions and form a
comparatively lower temperatures. More strikingly, the new product(s) with low enthalpy while releasing hydrogen.
desorption temperature could be lowered to even 50 1C Since the product is less stable as compared to the
when TiCl3 attached aerogels are employed for infiltra- reactants, a rapid reverse reaction pathway gets acceler-
tion experiments (Figure 12a (v)). Lot of promising research ated after completion of the reaction. As for example, the
has been done in this area and aerogels attracted composite system of LiBH4 and MgH2. The theoretical
special attention as nanoscafflod materials. Aerogels are hydrogen densities of these hydrides are 18.5 and 7.6 wt%.
considered the best option for nanoconfinement because The enthalpy values of these hydrides are also very high.
(i) areogels itself are hydrogen storage materials, (ii) they (DH of MgH2 is 75 kJ/mol H2 and LiBH4 is 70 kJ/mol H2)
are stable under a wide temperature and pressure range, i.e., bulk MgH2 must be heated to 300 1C in order to release
(iii) they possess deep open cages for trapping the hydrogen hydrogen at 1 bar. However when the composite ingredients
storage materials and (iv) aerogels itself catalyze the react with each other, 11.6 wt% hydrogen gets liberated in a
hydrides and functionalization of aerogels with other cata- single step.
lytic species is possible. 2LiBH4 ðlÞ þMgH2 ðsÞ-2LiHðsÞþMgB2 ðsÞ þ4H2 ðgÞ
Among the new hydrogen storage ideas, concepts related
ðhydrogen storage capacity is11:6 wt%Þ: ð44Þ
to mixing of two (or more) reactive hydrides attracted
High capacity hydrogen storage 583

Due to the formation of MgB2, the reaction enthalpy is advantages with regard to system design, handling etc.
reduced to DH = 46 kJ/mol H2 and the reversible hydrogen Extensive works have been carried out on unsaturated liquid
absorption become thermodynamically feasible. If the for- hydrocarbons but they are good candidates only above
ward reaction can be performed under manageable condi- 300 1C. In a recent breakthrough, Hull et al. [261] have
tions, this system/alike systems can open up a new shown that it is possible to include CO2 in the reversible
dimension in metal hydride research. Bösenberg et al. hydrogen storage through the reaction H2(aq.) +CO2
[256] have shown that it is possible to revert back the (aq.)2HCO2H (aq.). They have developed a promising
dehydrogenated composite system LiBH4 +MgH2 to its fullest Iridium based catalyst, through which hydrogenation of
hydrogen storage capacity. The authors showed that, addi- CO2 in the presence of hydroxide (basic aqueous conditions)
tion of either the bi-product MgB2 or a catalyst promotes can be done and the process can also be reverted. In
the rehydrogenation kinetics to a better extent. Figure 13 another breakthrough, Luo et al. [262] have synthesized
shows the comparative hydrogen absorption kinetics of the an air stable liquid hydride B–N methylcyclopentane which
RHCs, such as pristine LiBH4 + MgH2, 10 mol% MgB2 added can store hydrogen up to 4.7 wt%. The striking advantage
RHC, 5 mol% Sc2O3 added RHC, etc. at the reaction tem- of this compound is that, it is entirely a cyclic molecule
perature of 350 1C at 50 atm pressure. As seen, the reaction comprised of light weight atoms such as C, N, B and H.
of the catalyzed system gets completed within 3 h of Additionally it liberates hydrogen at 80 1C temperature
reaction time. Nielsen et al. [257] have confined the RHC with appreciable kinetics and the product does not undergo
in the pores (size 21 nm) of resorcinol formaldehyde any phase transformation. It has been demonstrated that
aerogel and observed dramatic forward as well reverse metal halide salts significantly catalyze its dehydrogenation
hydrogen sorption performances with utmost consistency. reaction. As seen in Figure 14, it is possible to get the
Recently many other new reactive hydride composite sys- liberation of almost 80% of the stored hydrogen using the
tems are also investigated by researchers [246,249,250]. A best catalyst within 5 min. The material can be processed to
patented work of Hayden et al. [258] provides hopes be reversible through an ethanol treatment. However,
through a Li–Mg–H system with high hydrogen storage presently the cost factor may spark questions regarding its
capacity. The general molecular formula of the system is large scale viability in commercial devices.
LixMgyHn, wherein x is in the range of 0.17–0.93, y is in the It appears that the hydrogen storage targets can be
range of 0.07–0.83 and n is not greater than x +2y. As we reached only through high capacity complex hydrides or
know, MgH2 stores 7.6 wt% with the equilibrium pressure of light weight binary/ternary hydrides. Thus it is clear that
1 atm at 300 1C, LiH stores 12.5 wt% with the equilibrium compounds formed by elements with atomic number less
pressure of 1 atm at 910 1C. By combining these two than about 20 have to be focused. Most of the well known
hydrides a series of new materials were developed with compounds falling under this category are very hygroscopic
appreciable capacity (as for e.g., Li0.76Mg0.24 stores in nature. Therefore, even after optimizing their hydrogen
10.6 wt%). It is also claimed that, a particular composition storage performances, the application potential shall be
in this class possesses considerable promise for reversible handicapped due to the air/moisture induced degradation.
hydrogen storage under manageable operating conditions. Recently, a breakthrough research report published by Jeon
How well will it impact the hydrogen research community et al. opened up new expectations to overcome this
remains to be seen. problem [263]. The authors showed how the air sensitive
Recently, liquid phase hydrogen storage materials also magnesium hydride can be embedded in a gas selective
attracted special attention, as for e.g., formic acid (HCO2H) polymer matrix called polymethyl metacrylate (PMMA). The
[259], hydrous hydrazine (N2H4  H2O) [260] etc. This is due
to the fact that liquid hydrides have several practical

Figure 13 The desorption characteristics of ‘‘Reactive Figure 14 Desorption kinetics of BN–methylcyclopentane

Hydride Composite’’ system LiBH4 + MgH2. Reproduced with enhanced by metal halides. Reproduced with permission from
permission from Ref. [256], Copyright& (2010) Elsevier. Ref. [262], Copyright& (2011) American Chemical Society.
584 D. Pukazhselvan et al.

AlH3. The above efforts give lot of scopes but the challenges will
fully be circumvented only if a breakthrough is achieved in
tailoring a high capacity reversible hydride which would be air-
stable, durable and quite well operative under affordable
conditions.

Conclusions

Metal hydride technology needs to be matured for the

successful realization of hydrogen economy. For stationary
applications, good number of STP hydrides is known pre-
sently so the technology can be treated as matured.
However, for portable device and mobile applications high
capacity hydrogen storage materials with better perfor-
mances need to be established. It is largely unlikely that any
of the pristine system known so far make a candidate of
choice. New material tailoring approaches like nanoconfine-
ment of high capacity hydrides, reactive hydride compo-
sites, in-situ catalysis of thermodynamically viable high
Figure 15 Pictorial representation of hydrogen permeation capacity hydrides are seemingly promising routes presently.
through MgH2 nanoparticles buried inside PMMA gas selective
polymer. Figure reveals that the system can be exposed to
air/moisture conditions and the MgH2 does not undergo con- Acknowledgment
tamination. Reproduced with permission from Ref. [263], Copy-
right& (2011) nature publishing group. The authors thank the Vice Chancellor Er. H.S. Chahal, Prof.
O.N. Srivastava, Prof. R.S. Tiwari and Dr. Sesha Srinivasan for
helpful discussions. D.P.S thanks UGC-India for Dr. D.S. Kothari
pictorial representation of MgH2 embedded PMMA gas post doctoral fellowship. V.K. thanks Department of Atomic
selective polymer is shown in Figure 15. The novelty of this Energy, Govt. of India for Senior Research Fellowship.
polymer is that, being a gas selective polymer, it does not
allow gases other than hydrogen to pass towards it because
the gas permeability property of the polymer suits only References
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High capacity hydrogen storage 589

[265] D.A. Mosher, S. Arsenault, X. Tang, D.L. Anton, Journal of S.K. Singh, Ph.D., is a professor & Chairman
Alloys and Compounds 446–447 (2007) 707. at the Dept. of Physics, D.C.R. University of
K. Sapru, S. Ramachandran, Z. Tan, E. Kurlonk, Proceedings Science & Technology, Murthal (Haryana),
of the 2001 DOE Hydrogen Program Review. India. He has been the founder Head of the
[266] S.M. Aceves, F. Espinosa-Loza, E. Ledesma-Orozco, T.O. Ross, Centre of Excellence for Energy and Envir-
A.H. Weisberg, T.C. Brunner, O. Kircher, International Journal onmental Studies in this university from
of Hydrogen Energy 35 (3) (2010) 1219. 2008 to date. Based upon his R&D contribu-
[267] SRNS News Room, SRNL Research Paves Way for Portable tion, Govt. of Haryana awarded first prize
Power Systems, /[Link] in Energy conservation to D.C.R.U.S.T in
[Link], 2012. 2009–2010. Presently, he is setting up Cen-
tre of Excellence for Renewable Energy test centre in the university
D. Pukazhselvan is presently UGC’s D.S. campus under sponsored project by DST Haryana. In a research
Kothari postdoctoral fellow at D.C.R. Uni- carrier spanning twenty years, he has published over thirty techni-
cal papers in international journals.
versity of Science & Technology. He pursued
his Ph.D. from Banaras Hindu University in
the area of high capacity hydrogen storage
materials. He has about 15 international
publications in peer reviewed journals. His
present research interests are in high capa-
city hydrogen storage, alternate energy,
electrochemistry and catalysis. He has
obtained post Ph.D. opportunity at University of Padova, Italy for
R&D works in high capacity hydrides. [contact info:
dpuksel@[Link]].

Vinod Kumar is presently a Senior Research

Fellow at D.C.R. University of Science &
Technology. He is pursuing his Ph.D. in
Hydrogen Storage & Applications. He did
his [Link]. in 2008 from MDU, Haryana and
was a rank holder during his Master’s
program.