International Journal of Hydrogen Energy 32 (2007) 1121 – 1140

www.elsevier.com/locate/ijhydene

Review
Metal hydride materials for solid hydrogen storage: A review夡
Billur Sakintuna a,∗ , Farida Lamari-Darkrim b , Michael Hirscher c
a GKSS Research Centre, Institute for Materials Research, Max-Planck-Str. 1, Geesthacht D-21502, Germany
b LIMHP-CNRS (UPR 1311), Université Paris 13, Avenue J. B. Clément, 93430 Villetaneuse, France
c Max-Planck-Institut für Metallforschung, Heisenbergstr. 3, D-70569 Stuttgart, Germany

Received 31 July 2006; received in revised form 21 November 2006; accepted 21 November 2006
Available online 16 January 2007

Abstract
Hydrogen is an ideal energy carrier which is considered for future transport, such as automotive applications. In this context storage of
hydrogen is one of the key challenges in developing hydrogen economy. The relatively advanced storage methods such as high-pressure gas
or liquid cannot fulfill future storage goals. Chemical or physically combined storage of hydrogen in other materials has potential advantages
over other storage methods. Intensive research has been done on metal hydrides recently for improvement of hydrogenation properties. The
present review reports recent developments of metal hydrides on properties including hydrogen-storage capacity, kinetics, cyclic behavior,
toxicity, pressure and thermal response. A group of Mg-based hydrides stand as promising candidate for competitive hydrogen storage with
reversible hydrogen capacity up to 7.6 wt% for on-board applications. Efforts have been devoted to these materials to decrease their desorption
temperature, enhance the kinetics and cycle life. The kinetics has been improved by adding an appropriate catalyst into the system and as well
as by ball-milling that introduces defects with improved surface properties. The studies reported promising results, such as improved kinetics
and lower decomposition temperatures, however, the state-of-the-art materials are still far from meeting the aimed target for their transport
applications. Therefore, further research work is needed to achieve the goal by improving development on hydrogenation, thermal and cyclic
behavior of metal hydrides.
䉷 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Hydrogen storage; Review; Mg-based hydrides; Complex hydrides; Intermetallic compounds; Ball-milling; Kinetics; Storage capacity; Operating
temperature and pressure

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1122
2. Mg-based metal hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123
2.1. Improvement on surface properties and mechanical ball-milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123
2.2. Cyclic stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127
2.3. Catalyst effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1128
2.4. Chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
3. Complex hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
3.1. Sodium alanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1130
3.2. Lithium and potassium alanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1131
3.3. Lithium nitrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1131
3.4. Lithium boro- and beryllium hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1132
4. Intermetallic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1135
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1136
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1136

夡 The work was carried out in LIMHP-CNRS.

∗ Corresponding author. Tel.: +49 (0) 4152 872673; fax: +49 (0) 4152 872670.
E-mail address: billur.sakintuna@gkss.de (B. Sakintuna).

0360-3199/$ - see front matter 䉷 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2006.11.022
1122 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
Nomenclature
BCC body centered cubic
BM ball-milling
Cyc. cycle
DOE US Department of Energy
H/M hydrogen atoms per metal atom
Mm misch metals
1. Introduction
Hydrogen is the ideal candidate as an energy carrier for both
mobile and stationary applications while averting adverse ef-
fects on the environment, and reducing dependence on imported
oil for countries without natural resources.
Hydrogen storage is clearly one of the key challenges in
developing hydrogen economy. Hydrogen can be stored as (i)
pressurized gas, (ii) cryogenic liquid, (iii) solid fuel as chemical
or physical combination with materials, such as metal hydrides,
complex hydrides and carbon materials, or produced on-board
the vehicle by reforming methanol [1]. Each of these options
possesses attractive attributes for hydrogen storage [2].
Available technologies permit directly to store hydrogen
by modifying its physical state in gaseous or liquid form in
pressurized or in cryogenic tanks. The traditional hydrogen-
storage facilities are complicated because of its low boiling
point (−252.87 ◦ C) and low density in the gaseous state
(0.08988 g/L) at 1 atm. Liquid hydrogen requires the addition
of a refrigeration unit to maintain a cryogenic state [3] thus
adding weight and energy costs, and a resultant 40% loss in
energy content [4]. High-pressure storage of hydrogen gas is
limited by the weight of the storage canisters and the potential
for developing leaks. Moreover, storage of hydrogen in liquid
or gaseous form poses important safety problems for on-board
transport applications. Designs involving the use of methane
as a hydrogen source require the addition of a steam reformer
to extract the hydrogen from the carbon which adds weight,
additional space requirements, and the need for a device to
sequester CO2 [1].
The US Department of Energy (DOE) [5] published a long-
term vision for hydrogen-storage applications considering eco-
nomic and environmental parameters. The predicted minimum
hydrogen-storage capacity should be 6.5 wt% and 65 g/L hy-
drogen available, at the decomposition temperature between 60
and 120 ◦ C for commercial viability. It was also predicted low
temperature of hydrogen desorption and low pressure of hydro-
gen absorption (a plateau pressure of the order of a few bars
at room temperature) and nonthermal transformation between
substrates and products of decomposition as reported by Schulz
[6]. Furthermore, the cost of a storage medium and its toxicity
properties need to be carefully considered for the realization of
the set goals.
Storage by absorption as chemical compounds or by ad-
sorption on carbon materials have definite advantages from the
P–C pressure-composition
Pabs hydrogen absorption pressure
Pdes hydrogen desorption pressure
Tabs hydrogen absorption temperature
Tdes hydrogen desorption temperature
tabs hydrogen absorption time
tdes hydrogen desorption time
XRD X-ray diffraction
safety perspective such that some form of conversion or energy
input is required to release the hydrogen for use. A great deal
of effort has been made on new hydrogen-storage systems, in-
cluding metal, chemical or complex hydrides and carbon nanos-
tructures.
Carbon materials such as activated carbons, carbon nan-
otubes, and carbon nanofibers have been the subject of intensive
research. The research on hydrogen storage in carbon materials
was dominated by announcements of high storage capacities
in carbon nanostructures. However, the experimental results on
hydrogen storage in carbon nanomaterials scatter over several
orders of magnitude. The hydrogen-storage capacity for car-
bon materials is reported between 0.2 and 10 wt% [7,8]. The
experiments to date claiming very high values could not inde-
pendently be reproduced in different laboratories. In view of
today’s knowledge although they have good reversibility prop-
erties, carbon nanostructures cannot store the amount of hydro-
gen required for automotive applications [9].
Hydrogen forms metal hydrides with some metals and alloys
leading to solid-state storage under moderate temperature
and pressure that gives them the important safety advantage
over the gas and liquid storage methods. Metal hydrides have
higher hydrogen-storage density (6.5 H atoms/cm3 for MgH2 )
than hydrogen gas (0.99 H atoms/cm3 ) or liquid hydrogen
(4.2 H atoms/cm3 ) [3]. Hence, metal hydride storage is a
safe, volume-efficient storage method for on-board vehicle
applications.
There are two possible ways of hydriding a metal, direct dis-
sociative chemisorption and electrochemical splitting of water.
These reactions are:
x
M + H2 ↔ MHx , (1)
2
x x x
M + H2 O + e− ↔ MHx + OH− , (2)
2 2 2
where M represents the metal.
Metal hydrides compose of metal atoms that constitute a host
lattice and hydrogen atoms. Metal and hydrogen usually form
two different kinds of hydrides, -phase at which only some
hydrogen is absorbed and -phase at which hydride is fully
formed. Hydrogen storage in metal hydrides depends on differ-
ent parameters and consists of several mechanistic steps. Met-
als differ in the ability to dissociate hydrogen, this ability being
dependent on surface structure, morphology and purity [10].
An optimum hydrogen-storage material is required to have the
 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
following properties; high hydrogen capacity per unit mass and
unit volume which determines the amount of available energy,
low dissociation temperature, moderate dissociation pressure,
low heat of formation in order to minimize the energy necessary
for hydrogen release, low heat dissipation during the exother-
mic hydride formation, reversibility, limited energy loss during
charge and discharge of hydrogen, fast kinetics, high stability
against O2 and moisture for long cycle life, cyclibility, low cost
of recycling and charging infrastructures and high safety.
Hydrogen-storage as metal hydride has been the focus of in-
tensive research. The hydrogen-storage systems have been re-
ported in numerous studies [11–17]. The light metals such as Li,
Be, Na, Mg, B and Al, form a large variety of metal–hydrogen
compounds. They are especially interesting due to their light
weight and the number of hydrogen atoms per metal atom,
which is in many cases at the order of H/M = 2. Heavier
ones may enter the multiple component system only as a low-
abundant additive, most likely for alteration of properties or as
a catalyst. There is enduring research both on modifying and
optimizing the known hydrogen-storage materials, and new re-
sources. The studies are conducted on finding optimum solid
hydrogen-storage system [18]. In this review, we briefly men-
tion about hydrogenation properties, advantages and disadvan-
tages of different metal-hydride systems such as Mg-based
metal hydrides, complex hydrides, alanates and intermetallic
compounds. A brief review of state-of-the art is reported on
metal hydrides. This work will serve to evaluate solid fuel
hydrogen store for industrial on-board hydrogen storage tank
design.
2. Mg-based metal hydrides
There is considerable research on magnesium and its alloys
for on-board hydrogen storage due to their high hydrogen-
storage capacity by weight and low cost [15]. Besides, the Mg-
based hydrides possess good-quality functional properties, such
as heat-resistance, vibration absorbing, reversibility and recy-
clability. In recent years, therefore, much attention has been
paid to investigations on specific material properties of Mg al-
loys for the development of new functional materials.
Magnesium hydride, MgH2 , has the highest energy density
(9 MJ/kg Mg) of all reversible hydrides applicable for hydrogen
storage. MgH2 combines a high H2 capacity of 7.7 wt% with the
benefit of the low cost of the abundantly available magnesium
[19–22] with good reversibility [23,24].
The main disadvantages of MgH2 as a hydrogen store is the
high temperature of hydrogen discharge, slow desorption kinet-
ics and a high reactivity toward air and oxygen [25,26]. Ther-
modynamic properties of the magnesium hydride system have
been investigated. The results showed high operating tempera-
ture which is too high for practical on-board applications [27].
High thermodynamic stability of MgH2 results in a relatively
high desorption enthalpy, which corresponds to an unfavorable
desorption temperature of 300 ◦ C at 1 bar H2 [15,20].
Hydrogen absorption/desorption properties of recently stud-
ied Mg-based hydrides are summarized in Table 1. Many efforts
has focused on Mg-based hydrides in recent years to reduce the
1123
desorption temperature and to fasten the re/dehydrogenation
reactions. These can be accomplished to some extent by chang-
ing the microstructure of the hydride by ball-milling (mechan-
ical alloying) with elements which reduce the stability of the
hydrides and also by using proper catalysts to improve the
absorption/desorption kinetics [61].
2.1. Improvement on surface properties and mechanical
ball-milling
A critical factor for hydrogen absorption by metals is
the metal surface, which activates dissociation of hydrogen
molecules and allows easy diffusion of hydrogen into the bulk.
Diffusion is not the limiting step initially because no material
has been reacted and there are sufficient active sites available
[62], but chemisorption is the slowest step for pure Mg at this
point [63]. As the reaction progresses, hydrogen diffusion takes
place and the hydride layer grows, producing a nearly imper-
meable layer. Diffusion through this hydride layer becomes
the rate-limiting step in the hydride formation process [63].
In addition to formation of a compact hydride layer, exposure
to oxygen also lowers absorption rates due to the formation
of a highly stable oxide layer [25]. Andreasen et al. [64] have
reviewed the kinetics in terms of apparent activation energies
and apparent prefactors of Mg-based hydrides. It was suggested
that variations in apparent activation energies correlate with the
presence of MgO surface layer inhibiting diffusion of hydrogen.
Thus, oxidized samples show large apparent activation energies
and well activated samples show smaller activation energies.
The ball-milling creating fresh surfaces during processing is
an economic process that is widely applied to metal hydrides
to achieve good surface properties [15]. The main effects
of ball-milling are increased surface area, formation of mi-
cro/nanostructures and creation of defects on the surface and
in the interior of the material. The induced lattice defects may
aid the diffusion of hydrogen in materials by providing many
sites with low activation energy of diffusion. The induced
microstrain assists diffusion by reducing the hysteresis of hy-
drogen absorption and desorption [30]. The increased surface
contact with catalyst during ball-milling leads to fast kinetics
of hydrogen transformations. It is possible to control proper-
ties of the store material, according to specific applications.
These include changing the alloy composition, surface prop-
erties, microstructures and grain size by ball-milling without
the additional cost of catalyst and with minimal loss of stor-
age capacity [58]. It is used for production of nanocrystalline
magnesium with superior powder morphology that gives re-
markable improvement of kinetics and surface activity for
hydrogenation [21,25]. The crystalline Mg2 Ni alloy obtained
by ball-milling has excellent surface properties compared with
those prepared by a conventional metallurgical method [65].
Huot et al. [58] investigated the structural difference between
milled and unmilled MgH2 . The specific surface area is de-
creased by milling 10-fold. Faster hydrogen desorption kinetics,
reduction in activation energy and enhanced kinetics observed
for the milled MgH2 compared to the unmilled one are seen in
Fig. 1. The activation energies for desorption were measured
 1124
Table 1
Hydrogen absorption/desorption properties of Mg-based hydrides

Material Method Temperature (◦ C) Pressure (bar) Kinetics (min) Cycling stability Max wt% of H2 Ref.

MgH2 –5 mol% Fe2 O3 BM Tabs : 300 Pabs : 2–15 tabs: 20 No data 1.37 [28]
30 wt% Mg–M mNi5−x (CoAlMn)x BM Tabs : 15 Pabs : 6 tabs : 83 No data 2.30 [22,29]
Mg–5 wt% FeTi1.2 BM Tabs and Tdes : 400 Pabs : 30 No data 9 cyc.: stable after fourth cycle 2.70 [30]
Pdes : 1
MgH2 –5 mol% V2 O5 BM Tabs : 250 Pabs : 15 tabs : 1.6 No data 3.20 [28]
90Mg–10Al BM Tabs and Tdes : 400 Pabs : 15 tabs : 2.7–19 No data 3.30 [31,32]
Pdes : 12 tdes : 0.5–5.8
Mg–50 wt% ZrFe1.4 Cr 0.6 BM Tabs : 250–350 Pabs : 20 tabs : 1 2 cyc.: stable 3.40 [33]
Tdes : 300–350 Pdes :1 tdes : 5
Mg–10 wt% CeO2 BM Tabs and Tdes : 300 Pabs : 11 tabs : 60 5 cyc.: not stable 3.43 [34]
Pdes : 0.5 tdes : 60
Mg–20 wt% Mm (La, Nd, Ce) BM (pellet form) Tabs : 300 Pabs : 10 tabs : 10 No data 3.50 [35]
Tdes : 480 Pdes : 1 tdes : 5
Mg–40 wt% ZrFe1.4 Cr 0.6 BM Tdes : 270–280 Pdes : 1 tdes : 15 2 cyc.: stable 3.60 [36]
La2 Mg17 –40 wt% LaNi5 BM Tabs and Tdes : 250–303 Pabs and Pdes : 4–7 tabs : 0.45 20 cyc.: not stable 3.70 [37,38]
tdes : 4
La0.5 Ni1.5 Mg17 Hydriding combustion Tabs and Tdes : 280–400 Pabs : 2.21–11.34 tabs : 15 Not stable 4.03 [39]
synthesis
Pdes : 1.62–15.48 tdes : 5
Mg–50 wt% LaNi5 BM Tdes : 250–300 Pabs and Pdes : 10–15 tabs : 3.33 Not stable 4.10 [40]
MgH2 –2LiNH2 BM Tabs and Tdes : 200 Pabs : 50 tdes : 60 4 cyc.: stable after 2nd cycle 4.30 [41,42]
Pdes : 10
Mg2 CoH5 Mixing Tabs : 450–550 Pabs : 17–25 No data 1000 cyc.: stable 4.48 [43]
MgH2 –5 mol% Al2 O3 BM Tabs : 300 Pabs : 15 tabs : 67 No data 4.49 [28]
1.1MgH2 –2LiNH2 BM Tabs : 200 Pabs : 30 Tabs : 30 9 cyc.: stable 4.50 [44,45]
Mg–20 wt% TiO2 BM Tabs : 350 Pabs : 20 bar tabs : 2 No data 4.70 [46]
Tdes : 330–350 Pdes : 1 tdes : 10
Mg–30 wt% BM (hexane medium) Tdes : 300–550 Pdes : 2 tdes : 30 No data 5.00 [47]
MmNi4.6 Fe0.4
MgH2 –5 wt% V BM Tabs and Tdes : 300 Pabs and Pdes :1–3 tabs : 2 2000 cyc.: stable 5.00 [48]
tdes : 10
Mg–Fe–Mg2 FeH6 Mixing Tabs : 473–552 Pabs : 77–85 tabs : 90 600 cyc.: stable 5.00 [43]
MgH2 –Mg2 FeH6 Mixing Tabs and Tdes : 350–525 Pabs and Pdes : 3.6–93.7 tabs : 90–1440 600 cyc.: stable 5.00 [49]
MgH2 –5 at% Ti BM Tabs : 200 Pabs : 10 tdes: 3.33 No data 5.00 [50]
B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140

Tdes : 300 Pdes : 0.15 tabs : 0.83

MgH2 –5 at% Ni BM Tabs : 200 Pabs : 10 tdes : 5 No data 5.00 [50]
Tdes : 300 Pdes : 0.15 tabs : 16.7
Mg–30 wt% LaNi2.28 BM Tabs : 280 Pabs : 30 tabs : 1.6 3 cyc.: stable 5.40 [51]
MgH2 –5 at% V BM Tabs : 200 Pdes : 0.15 tdes : 3.33 No data 5.50 [50]
Tdes : 300 Pabs : 10 tabs :1.66
Mg–10 wt% Fe2 O3 BM Tabs : 320 Pabs : 12 tabs : 60 3 cyc.: stable 5.56 [52]
tabs : 10
Mg–30 wt% CFMmNi5 Mixing and Tabs and Tdes : 500 Pabs and Pdes : 3–10 tdes: 40 No data 5.60 [53]
encapsulation
Mg–10 wt% Al2 O3 BM Tabs and Tdes : 300 Pabs : 11 tabs : 60 5 cyc.: not stable 5.66 [34]
Pdes : 0.5 tdes : 60
 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1125
[54]

[34]

[43]
[50]

[55]

[56]
[57]

[58]

[59]
[26]

[20]

[60]
 7.60
5.80

5.87

6.00
6.00

6.40

6.50
6.70

7.00

7.00
7.00

7.30
5 cyc.: not stable

2 cyc.: not stable

1000 cyc.: stable
800 cyc.: stable
No data

No data

No data

No data

No data
No data

No data

No data
tdes : 50 (unmilled)
tdes : 12.5 (milled)
tdes : 10–35
tabs : 13.33
tdes : 8.33

tdes : 150

tabs : 420
No data

No data
tabs: 4.2

tdes: 1.5
tdes : 33
tabs : 60
tdes : 60
tabs: 90

tabs : 6

tabs : 2

tabs : 1
tdes: 6

Fig. 1. Hydrogen desorption curves of unmilled MgH2 (solid symbols) and

ball-milled (hollow symbols) MgH2 under a hydrogen pressure of 0.15 bar
[58].
Pabs and Pdes : 4.0–1.4

Pabs and Pdes : 1–2

as 120 and 156 kJ/mol for the milled and unmilled powders,
respectively. It has been found that ball-milling of Mg2 NiH4
vacuum

vacuum
3–10

substantially decreases the desorption temperature. Depending

Pdes : 0.15

0.15
Pdes: 0.15
Pdes : 0.5

8.4

8.4

0.6
Pabs : 10

Pabs : 11

Pabs : 10

No data
1

on the ball-milling conditions, the shift of the onset of desorp-

Pdes :
Pabs :
Pdes :
Pabs :
Pdes :
Pdes :
Pabs :
Pdes :
Pabs :

tion temperature can be as large as 100 ◦ C for MgH2 and 40 ◦ C

for Mg2 NiH4 [66].
Hydrogenation properties are very sensitive to these surface
modifications. The ball-milled powders do not require activa-
Tabs and Tdes : 300

Tabs and Tdes : 300

Tabs and Tdes : 300

Tabs : 300 (milled)

Tdes : 350 (milled)

Tabs andTdes : 300

tion compared to the conventional methods. For all nanocrys-

Tabs : 230–370

Tdes : 150–250

Tdes : 140–190

Tdes : 335–347
Tdes : 50–150

talline hydrides investigated, the grain boundary does not

Tabs : 200
Tdes : 300

Tabs : 200
Tdes : 300

Tabs : 180

dramatically affect the pressure–composition (P–C) isotherms.

This describes the thermodynamic aspects of hydride forma-
tion which is more visible in the Van’t Hoff plots that illustrate
the relationship between equilibrium pressure and changes in
enthalpy and entropy. The pressure for hydrogen desorption
cyclohexane medium)
Wet-chemical method

of the unmilled MgH2 is lower than that of the milled one, as

BM (benzene and

seen in Fig. 2.
Aoyagi et al. [67] proposed that ball-milling of the alloys
under inert environment leads to reduction in powder size and
Mixing

creation of new surfaces, which are effective for the improve-

BM

BM

BM

BM

BM
BM

BM

BM

BM

ment of the hydrogen absorption rate. Hydrogen absorption

rate of Mg-based alloys also increases with the milling time.
Liang et al. [30] proposed that ball-milling of Mg–5 wt%
MgH2 –0.2 mol% Cr 2 O3

MgH2 –1 mol% Cr 2 O3
Mg/MgH2 –5 wt% Ni

FeTi1.2 produces fine powder with nanometer-sized grains and

Mg–0.5 wt% Nb2 O5
Mg–10 wt% Cr 2 O3

3Mg(NH2 )2 –8LiH
MgH2 –2 mol% Ni
MgH2 –5 at% Mn

large microstrain, which results in an increase in the hydrid-

MgH2 –5 at% Ge
MgH2 –5 wt% V

MgH2 –1 at% Al

ing and dehydriding rates. The high absorption rate is due to

the large quantity of phase boundaries and the porous surface
MgH2

structure [40]. Nanocrystalline hydrides enhanced the hydro-

genation kinetics, even at relatively low temperatures. These
1126 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
Fig. 2. Pressure–concentration–temperature curves of the unmilled and
ball-milled MgH2 at 623 K [58].
structures can be obtained by means of local change in the
stable atomic positions into the metastable configuration.
Ball-milling of LiNH2 /MgH2 results in low dehydrogenation
temperature (200 ◦ C) but with markedly slow kinetics and
lowered hydrogen uptake capacity [41]. Wagemans et al. [68]
investigated the quantum chemical perspective of MgH2 . Small
MgH2 clusters have much lower desorption energy than bulk
MgH2 , hence enabling hydrogen desorption at lower tempera-
tures. The hydrogen desorption energy decreases significantly
when the crystal grain size becomes smaller than 1.3 nm. A
MgH2 crystallite size of 0.9 nm corresponds to a desorption
temperature of only 200 ◦ C [68]. Particles with nanocrystalline
structure with grain size of 10 nm or less, increase the density
of grain boundaries, resulting in easier activation [69].
In another approach, a hydrogen-absorbing material can be
hydrogenated during ball-milling [70]. It was shown that ball-
milling under hydrogen atmosphere is a convenient method for
the formation of metal hydrides which causes simultaneous hy-
drogen uptake and mechanical deformation resulting from ball-
milling. Huot et al. [71] produced MgH2 under H2 atmosphere
by ball-milling. This method improved the hydride formation
kinetics. Chen et al. [72] studied also the formation of metal
hydrides under H2 atmosphere. The results indicated that pul-
verization and deformation processes occurring during high-
energy ball-milling play a major role in the hydriding reaction.
It is concluded that ball-milling is a simple and inexpensive
method of producing high hydrogen content metal hydrides.
Mg–10 wt% Fe2 O3 is synthesized by mechanical grinding
under H2 atmosphere [52]. It increases the H2 -sorption rates
Fig. 3. Desorption curves of magnesium catalyzed with 0.1 mol% Nb2 O5 and
milled for 2, 5, 10, 20, 50 and 100 h, at 573 K and vacuum [75].
with 5.56 wt% H2 absorption, by facilitating nucleation by cre-
ating defects on the surface of Mg particles and reducing the
particle size of Mg and thus by shortening the diffusion dis-
tances of hydrogen atoms. By using the same method, it was
proposed recently that the presence of nickel lowered the onset
temperature of MgH2 desorption to 225 ◦ C by ball-milling un-
der hydrogen atmosphere [71]. Tessier et al. [70] synthesized
Mg2 Ni with the same method. Furthermore, Orimo et al. [73]
found that ball-milling of Mg2 Ni under hydrogen resulted in
a significant facilitation of hydrogen desorption. Alloying time
has a significant effect on hydride properties of Mg2 Ni. Ab-
dellaoui et al. [74] proposed that absorption capacity changes
with alloying duration. Barkhordarian et al. [75] investigated
the effect of milling time on the magnesium hydrogen sorp-
tion reaction. Reaction kinetics is enhanced by increasing the
milling time, as shown in Fig. 3. Ball-milling is generally used
to produce powders in the range of 60.100 m [25,76] to cre-
ate more active sights for hydrogen penetration. Smaller parti-
cle sizes also eliminate the formation of hydride layers greater
than 50 m [25].
Although extensive work has been done on hydrogen storage
in bulk materials as thin film hydride is an emerging field of
research. Research performed on thin films of pure magnesium
concluded that the thinner the magnesium sheet, the faster it
achieved complete formation of MgH2 . It was found that hy-
drogen penetrated to an average depth of 30 m and stopped
[77]. Mg portions of the film have converted totally into MgH2
at temperatures not higher than 200 ◦ C [78]. Hydrogen-storage
properties of nanocomposite three-layered Pd/Mg/Pd films
have been previously investigated. After hydrogenation under
a hydrogen gas pressure of 1 bar at 100 ◦ C, Pd layers contain
only 0.15–0.30 wt% H2 , whereas the Mg film contains 5.0 wt%
hydrogen [79]. Pd/Mg films with different degree of crystal-
lization in the Mg layer are prepared in different sputtering
conditions [77]. The dehydriding temperature decreases with
decreasing the degree of crystallization in the Mg layer in
 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1127

Table 2
Hydrogen absorption/desorption properties of Mg–Ni-based hydrides

Material Method Temperature (◦ C) Pressure (bar) Kinetics (min) Cycling stability Max wt% of H2 Ref.

Mg2 Ni–1 wt% Pd BM Tabs : 200 Pabs : 15 tabs : 27 4 cyc.: stable 2.50 [86]
Mg2 Ni BM Tabs : 300 Pabs : 29 5 cyc.: not stable 3.20 [87]
Mg2 Ni BM Tabs : 300 Pabs : 11.6 tabs : 10 4 cyc.: stable 3.50 [86]
Mg2 Ni BM Tabs and Tdes : 280 Pdes : 1–2 No data No data 3.53 [74,88]
Mg–Mg2 Ni BM Tabs : 300 Pabs : 12 tabs : 83 2 cyc.: not stable 3.60 [89]
Mg2 Ni BM Tabs and Tdes : 280–330 Pabs : 1–15 tabs : 1 No data 4.10 [82]
Pdes : 1–2 tdes : 1
70 wt% Mg–30 wt% LaNi5 BM Tabs and Tdes : 350 Pabs : 10 tabs : 30 10 cyc.: stable 4.66 [90]
Pdes : 1.5 tdes : 10 [91]
65 wt% MgH2 –35 wt% Mg2 NiH4 BM Tdes : 220–240 Pdes : 0.5 tabs : 10 20 cyc.: stable 5.00 [66]

Pd/Mg films. The lowest crystallization of films absorb 5.6 wt%
of hydrogen and all hydrogen desorbed at a temperature lower
than 190 ◦ C in a vacuum [77].
Mechanical alloying can be preformed in the presence of or-
ganic solvents such as benzene, cyclohexane or carbon materi-
als [80,81]. Nanosized MgH2 ball-milled with benzene showed
reversible hydriding/dehydriding with high capacity under 1 bar
hydrogen pressure. It was proposed that the organic additives
of benzene or cyclohexane are essential for decisive character-
istics of the resulting magnesium to sustain nanosized magne-
sium with high-degree of dispersion [20]. Wet milling in the
presence of toluene leads to hydrogen and carbon pick up in the
powder, and also require much longer milling times [82]. Hy-
driding properties of Mg-based composites which are prepared
by mechanical milling of magnesium powder and graphite or
graphite supporting 5 wt% Pd in the presence of various ad-
ditives (tetrahydrofuran, benzene or cyclohexane) have been
studied [80]. In particular, the presence of tetrahydrofuran in
the milling process strongly affected the hydriding and dehy-
driding kinetics of the resulting composites [80]. There is a
synergetic interaction between Mg and aromatic carbon atoms
of graphite containing charge transfer to some extent.
It has been found that the hydrogenation properties of Mg,
such as hydrogenation/dehydrogenation temperature and hy-
drogenation rate, can be more or less improved by forming
composite structures. Zhu et al. [22,29] reported that the hy-
drogen sorption properties of Mg and Mg–Ni-based alloys can
significantly be improved by forming composites having proper
microstructural feature.
Mg2 NiH4 attracts wide interest for being a promising hydro-
gen store material due to its relatively high capacity, low cost,
light weight and low-toxicity [83] and for its unusual struc-
tural and bonding properties [84,85]. The hydrogen absorption
and desorption properties of Mg–Ni-based alloys are listed in
Table 2. Mg2 NiH4 forms eagerly by hydrogenating the alloy
Mg2 Ni [92]:
Mg2 Ni + 2H2 → Mg2 NiH4 .
Upon hydrogenation, Mg2 Ni reacts with 3.6 wt% of hydro-
gen and transforms into the hydride phase, Mg2 NiH4 , and the
dehydriding temperature is 250.300 ◦ C at desorption pressure
of 2.1–3.0 bar [22,66,74,84,88]. High hydrogen capacity of four
hydrogen atoms per Mg2 Ni, combined with the small specific
weight of the alloy is the most important advantage of Mg2 Ni
over other magnesium hydrides [93].
There are numerous publications regarding the upgrade of
hydrogenation properties of Mg2 NiH4 . Their hydriding prop-
erties are thought to be strongly affected by their nanometer-
scale structures by means of thermodynamic and kinetic
aspects. MgNi2 prepared by ball-milling is found to react with
hydrogen even at room temperature, whereas polycrystalline
material needs hydrogenation temperature of 250.350 ◦ C and
pressure of 15–50 bar [84]. Haussermann et al. [92] inves-
tigated the structural stability and bonding properties of the
Mg2 NiH4 using ab initio density functional calculations. Par-
ticular changes of the hydriding properties of the nanostruc-
tured Mg2 NiH4 have been also reported [19,22,25,73,94].
The nanocrystalline Mg2 Ni intermetallic compound formed
by mechanical alloying of Mg and Mg2 Ni can absorb hydro-
gen rapidly without activation. The Mg + Mg2 Ni composites
need activation, but once activated, they absorb hydrogen more
rapidly than Mg2 Ni at low temperature of 150 ◦ C under 12 bar
with high capacity of 4.2 wt% [89]. Nanoparticles of Mg2 Ni
leads to superior hydrogenation behavior including easy acti-
vation and hydrogen uptake in the first cycle itself compared to
the conventional crystal phase [86,87]. Nanocrystalline Mg2 Ni
with Pd exhibits much faster absorption kinetics at 200 ◦ C than
the as-ball-milled samples (reaction halftime of 2 and 33 min,
respectively) [86].
2.2. Cyclic stability
Cyclic stability is one of the major criteria for applicability
of metal/metal hydride systems for reversible hydrogen storage.
Depending on the nature of the additives, cycling temperatures
and starting microstructures, various structures and intermedi-
(3) ate phases can be obtained. Song et al. [34] synthesized magne-
sium hydrides with additives of Cr 2 O3 , Al2 O3 and CeO2 . All
the samples absorb and desorb less hydrogen at the fifth cycle
than at the first cycle due to the agglomeration of the particles
1128 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
Fig. 4. Cyclic stability of chemical Ni-doped Mg at 503–643 K and 4.0 bar,
time for one full cycle 3 h [43].
during hydrogenation/dehydrogenation cycling. Misch metals
(Mm) such as Ce, La, Nd and Pr, are used to increase the cyclic
stability [95,35]. However, the increased concentration of Mm
in the samples has an adverse effect on hydrogen-storage ca-
pacity and their reaction rate [35]. Gross et al. [37] have re-
ported formation phase changes, segregation and disintegration
of La2 Mg17 + 40 wt% LaNi5 during cycling at temperatures
up to 350 ◦ C. It was also reported that hydrogen capacity of
La0.5 Ni1.5 Mg17 decreases with cycling [39].
There are few publications regarding high number of cyclic
tests. Reiser et al. [43] investigated the behavior of Ni-doped
Mg and Mg2 CoH5 . They indicated that they are almost stable
even after 800 cycles with small fluctuations in the hydrogen ca-
pacity, as shown in Fig. 4. The cyclic stability of MgH2 –5 wt%
V is studied by Dehouche et al. [48] up to 2000 cycles. They
concluded that there is no change in isotherms and no disinte-
gration of the materials even when hydrogen content reached
5 wt%. Also the cyclic stability of MgH2 + 0.2 mol% Cr 2 O3 is
previously examined at 1000 cycles. Although desorption time
is increased, an increase of H2 storage capacity is reported by
about 8% between the first and the 500 or 1000 cycle due to
structural relaxations and crystallite growth [55]. Friedlmeier
et al. [96] observed a decrease in the kinetics of hydrogen ab-
sorption after 4300 cycles, but no loss in the hydrogen capacity
of Mg–2 at% Ni alloy. However, to achieve the same storage
capacity, the system temperature had to be increased. Neverthe-
less, Dehouche et al. [97] showed 15% decrease in hydrogen
capacity after 2100 cycles with a starting material of nanocrys-
talline Mg2 Ni. This was attributed to the formation of the non-
hydride forming MgNi2 phase, during the cycling process.
The resistance of metal hydrides to impurities is one of the
critical issues for on-board applications in order to maintain
performance over the lifetime of the material. The effects of
N2 , O2 , CO2 and CO on a pure magnesium powder have been
studied [98]. Both O2 and N2 slowed the rate of hydrogen ab-
sorption, while CO and CO2 entirely prevented the uptake of
hydrogen [98,99]. The performance of MgH2 .V.Ti was eval-
uated after 1000 cycles under a H2 atmosphere containing
101 ppm moisture. Hydrogen-storage capacity increased 5% but
desorption properties deteriorated due to surface modification
of the particles [100].
2.3. Catalyst effect
Catalysis is one of the critical factors in the improvement
of hydrogen sorption kinetics in metal hydride systems that
enables fast and effective dissociation of hydrogen molecules
[21]. Effective catalysts, even added in small amounts enhance
the formation of a hydride in reasonable extent. There is in-
tensive research about finding a proper catalyst to enhance the
hydriding properties. It was reported that the rate of absorption
is controlled by the following factors: the rate of hydrogen dis-
sociation at the surface, the capability of hydrogen to penetrate
from the surface which is typically covered by an oxide layer
into metal, the rate of hydrogen diffusion into the bulk metal
and through the hydride already formed.
Palladium is a good catalyst for hydrogen dissociation re-
action. The hydriding properties are enhanced by catalysis
through nanoparticles of Pd located on magnesium surface
[25]. The reactivity of palladium after exposure to oxygen is
recovered during exposure to hydrogen because of the easy
decomposition of palladium oxide [93]. However, high cost
of palladium is the main disadvantage for the industrial ap-
plications [15]. Zaluski et al. [86] have also reported on the
presence of Pd as a catalyst in nanocrystalline Mg2 Ni, LaNi5
and FeTi systems, enhance the absorption rates even at lower
temperatures and maintain less sensitivity to air exposures.
Hydrogen molecules have a strong affinity for nickel and
readily dissociate and adsorb onto surface-layer nickel clusters
[101,102]. Through the addition of 1 at% of nickel to magne-
sium, Holtz and Imam [76] achieved a 50% increase in hy-
drogen capacity, a decrease in the temperature for the onset of
hydrogenation from 275 to 175 ◦ C, and a lowering of the de-
hydrogenation onset temperature from 350 to 275 ◦ C.
In addition to Pd and Ni, Ge can be used for the catalysis
of hydrogenation kinetics [60]. The presence of Ge decreases
the hydride decomposition temperature in a range from 50 to
150 ◦ C, depending on the catalyst amount. But the catalytic ef-
fect of Ge disappears after few hydrogen absorption/desorption
cycles [60]. Vanadium also acts as a catalyst for the dissoci-
ation of hydrogen molecules. It was also reported using V as
a catalyst, hydrogen capacity can be increased up to 5.8 wt%
while the thermodynamic parameters of MgH2 were not altered
[54], as shown in Fig. 5.
Titanium and vanadium block the oxidation of the alloy sur-
face, and therefore, increase the discharge capacity over mul-
tiple cycles [103]. A nanocrystalline Mg1.9 Ti0.1 Ni alloy shows
good absorption kinetics at room temperature [104]. The Ti de-
creases the kinetic barriers of absorption while the Ni protects
the alloy from deactivation due to oxide layer formation.
The poor kinetics of MgH2 are greatly improved by addition
of different oxide catalysts that enhance hydriding properties
at relatively low temperature, such as V2 O5 [28] and Cr 2 O3
[34,55]. The oxide particles may operate as a milling ball dur-
ing high-energy ball-milling that creates many defects in the
Mg powder. Defects provide hydrogen an easy path to Mg [28].
It was also proposed that Cr 2 O3 yields fast hydrogen absorp-
tion, whereas V2 O5 and Fe3 O4 cause the most rapid desorp-
tion of hydrogen [57]. The addition of TiO2 also resulted in
 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
Fig. 5. Hydrogen desorption curves of mechanically milled MgH2 –5 at% V
composite (hollow symbols) and MgH2 (solid symbols) under 0.15 bar [54].
a markedly improved hydrogenation performance of Mg, rapid
kinetics, low working temperature and excellent oxidation re-
sistance [46]. Liang et al. [40] suggested that La showed a cat-
alytic effect on Mg–50 wt% LaNi5 nanocomposite.
In addition to catalyst type, the amount of catalysts used
has a significant effect on hydrogen absorption behavior.
Oelerich et al. [57] investigated different amounts of oxides
for catalysis but it is shown that only 0.2 mol% of the cata-
lyst is sufficient to provide fast sorption kinetics. The effect
of Nb2 O5 concentration on the kinetics of magnesium hydro-
gen sorption reaction at 300 ◦ C is studied. Fastest kinetics are
obtained using 0.5 mol% Nb2 O5 with a 7.0 wt% of hydrogen
capacity [26].
In the search for efficient and inexpensive catalysts for hy-
drogen sorption reactions, a new type of catalytic compounds
is developed [105]. These catalytic complexes demonstrated re-
markable enhancement in sodium alanates and magnesium, as
well as in hydrogen generation through hydrolysis [105].
2.4. Chemical composition
The type and the chemical composition of the metal alloy
is one of the most important factors in the metal–hydrogen
system [21]. Bouaricha et al. [31] prepared Mg/Al alloys by
high-energy ball-milling. The measured hydrogen capacity of
the material decreases with Al content, from H/M = 1.74 for
pure unmilled Mg, to 1.38 for Mg:Al (90:10), and then to 1.05
for Mg:Al (75:25). But it improves the kinetics. Ball-milling has
a possibility to combine two or more phases having different
hydrogenation characteristics [21].
1129
Wang et al. [33,36] combined both the catalytic and milling
effect in a system of fine ZrFe1.4 Cr 0.6 particles covering
Mg particles that resulted in an enhancement in absorp-
tion/desorption rates. ZrFe1.4 Cr 0.6 dispersing homogeneously
on the particle surfaces and in the interior of the material played
an important role in promoting the decomposition of MgH2 .
That probably could account for the decrease in activation en-
ergy. In another study [51], mechanically alloyed Mg–30 wt%
LaNi2.28 reported to have good hydriding properties with
5.40 wt% hydrogen storage under 30 bar hydrogen pressure.
With energetic ball-milling, the solubility limit of magne-
sium in lithium slightly increased [106]. Luo [44] developed
LiNH2 /MgH2 system by partial substitution of Li by Mg which
has a storage capacity of 4.5 wt% at 200 ◦ C and 30 bar. Me-
chanical alloying of Mg with some elements such as Zn, Al,
Ag, Ga, In or Cd resulted in reducing the stability of magne-
sium hydride. Indium and cadmium gave the best results [107].
Bogdanovic et al. [49] and Reiser et al. [43] considered the
Mg2 FeH6 –MgH2 systems. The maximum amount of stored hy-
drogen is 5.0 wt% which is one third less than magnesium dihy-
dride with 7.7 wt%, but the Mg2 FeH6 .MgH2 system possesses
numerous advantages including the low price of starting mate-
rials, the free choice and constancy of the heat delivery temper-
ature by controlling the applied hydrogen pressure and absence
of heat losses with time. The intermetallic hydride Mg2 FeH6
shows the high volumetric hydrogen density of 150 kgH2 /m3 ,
which is more than double of liquid hydrogen [108].
Nanocomposites of MgH2 and 3d transition metals, Ti, V,
Mn, Fe and Ni, have been investigated intensively [48,50,109].
The composites containing Mg–Ti and Mg–V exhibited the
rapid absorption kinetics such as absorption time of 2–5 min.
Formation enthalpy and entropy of magnesium hydride is dis-
torted by milling with transition metals. Furthermore, the acti-
vation energy of desorption for magnesium hydride is reduced
at 200 ◦ C.
3. Complex hydrides
Another class of light-weight storage materials is com-
plex hydrides. Complex hydrides are known as “one-pass”
hydrogen-storage systems which mean that H2 evolves upon
contact with water. Sodium, lithium and beryllium are the only
elements lighter than magnesium that can also form solid-state
compounds with hydrogen. The hydrogen content reaches the
value of 18 wt% for LiBH4 . Use of complex hydrides for
hydrogen storage is challenging because of both kinetic and
thermodynamic limitations.
Intense interest has developed in low weight complex hy-
drides such as alanates [AlH4 ]− , amides [NH2 ]− , imides and
borohydrides [BH4 ]− . In such systems, the hydrogen is often
located at the corners of a tetrahedron. The alanates and borates
are especially interesting because of their light weight and the
capacity for large number of hydrogen atoms per metal atom.
Borates are known to be stable and decompose only at ele-
vated temperatures. Alanates are remarkable due to their high
storage capacities; however, they decompose in two steps upon
dehydriding.
1130 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
3.1. Sodium alanates
Sodium alanates are complex hydrides of aluminum and
sodium. Sodium tetrahydroaluminate–NaAlH4 and trisodium
hexahydroaluminate–Na3 AlH6 have been known for decades.
Sodium aluminum hydride, NaAlH4 , would seem to be a
possible candidate for application as a practical on-board
hydrogen-storage material due to the theoretically reversible
hydrogen-storage capacity of 5.6 wt%, low cost and its avail-
ability in bulk.
Although they have good hydrogen-storage capacity, com-
plex aluminum hydrides are not considered as rechargeable
hydrogen carriers due to irreversibility and poor kinetics.
However, by using appropriate transition or rare-earth metals
as catalysts, the complex hydrides can be made reversible.
Bogdanovic and Schwickardi [110,111] demonstrated upon
doping with proper titanium compounds, the dehydriding of
aluminum hydrides could be kinetically enhanced and main-
tain reversibility under moderate conditions in the solid state.
Unlike intermetallic hydrides, these complex-based hydrides
release hydrogen through a series of decomposition reactions
as described in two equations below, for the dehydrogenation
reactions of NaAlH4 :
NaAlH4 ↔ 13 Na3 AlH6 + 23 Al + H2 , (4a)
Na3 AlH6 ↔ 3NaH + Al + 23 H2 . (4b)
Theoretically, NaAlH4 and Na3 AlH6 contain large amounts
of hydrogen, 7.4 and 5.9 wt%, respectively. However, the re-
lease of hydrogen does not occur in a single-step reaction.
NaAlH4 first decomposes evolving molecular hydrogen and
form an intermediate compound, Na3 AlH6 and metallic Al.
This intermediate phase then decomposes to NaH with ad-
ditional metallic Al formation and hydrogen evolution. The
reversibility of these two reactions is a critical factor for the
practical applications.
Stoichiometrically, the first step consists of 3.7 wt% H2 re-
lease and the second step 1.9 wt%, for a theoretical net reaction
of 5.6 wt% reversible gravimetric hydrogen storage [111,112].
The process is characterized by slow kinetics and reversibility
only under severe conditions. The operating temperatures are
between 185 and 230 ◦ C, and 260 ◦ C for the first and the sec-
ond reaction, respectively. Finally, the decomposition of NaH
occurs at a much higher temperature, with the total hydrogen
release of 7.40 wt%. For hydrogen storage, only the first two
reactions need to be considered, because the decomposition of
NaH occurs at too high temperature of 425 ◦ C for practical
storage systems.
Previously Jensen et al. [113] reviewed the catalytically en-
hanced sodium aluminum hydrides. Recently, numerous stud-
ies are being carried out to enhance the hydriding properties of
NaAlH4 as listed in Table 3.
The effects of liquid alkoxides Ti(Obun )4 + Zr(OPr i )4 on
hydriding properties of sodium alanates were investigated
by Sandrock et al. [116]. The liquid alkoxides contribute
to hydrocarbon contamination of the released hydrogen.
Moreover the surface of sodium alanate is damaged by the
catalyst which causes decreasing the cyclic capacity.
The dry-doping TiCl3 catalyst is investigated by the same
group [123]. It largely eliminates the high catalyst weight,
low capacity and contamination problems noted above for the
alkoxide catalysts [116]. Both the hydriding and dehydriding
rates increases by doping [123]. Under the same rehydrogena-
tion conditions, the amount of evolved hydrogen from the
Ti-doped NaAlH4 is about 50 times as much as that of the
undoped NaAlH4 . This clearly indicates that the addition of ti-
tanium species enhances kinetically not only the dehydrogena-
tion, but also the rehydrogenation reaction of NaAlH4 [118].
With 2 mol% TiN as a doping agent, cyclic storage capacity
of 5 wt% H2 is achieved after 17 cycles. However, decrease in
hydrogenation rate with number of cycles is observed [122].
Zirconium doping is also used for the same purpose. The dehy-
driding kinetics of NaAlH4 is significantly improved. Although
effects of zirconium are poorer than titanium as a catalyst for
the dehydriding of NaAlH4 to Na3 AlH6 and Al, it is a superior
catalyst for the dehydriding of Na3 AlH6 to NaH and Al [119].
Sun et al. [124] examined the details of the doping role
of titanium and zirconium on NaAlH4 with XRD. Significant
changes occur in the lattice parameters of sodium alanates upon
doping. Hence the enhancement of dehydriding kinetics is as-
sociated with dopant induced lattice distortions rather than the
catalytic effect [124]. Phase transitions and crystal structure
modifications of doped-NaAlH4 were also observed by Gross
et al. [125]. Contrary to Sun et al. [124], they proposed the cat-
alytic effects of doping materials in the enhancement of kinet-
ics of NaAlH4 . It was earlier reported that the presence of Ti is
not enough rather a particular local arrangement is required for
the dehydrogenation reaction [126]. Ti-cluster-doped NaAlH4
is investigated [122,127]. The hydrogenation and dehydrogena-
tion measurements indicate that the state of the precursor is of
even greater importance than the simple amount of Ti in the
material. The small size of the Ti clusters seem to be responsi-
ble for the increase of the reaction rate [127].
Although titanium has positive effects as a catalyst, kinet-
ics is not fully enhanced. The hydrogen desorption can last
up to 4200 min in some cases [123]. To improve the kinet-
ics Thomas et al. [128] investigated the effects of mechanical
ball-milling on the microstructural character of NaAlH4 in the
presence of catalyst. Fracture and fragmentation of particles
are observed in particle morphology. The direct synthesis of
Na3 AlH6 and Na2 LiAlH6 by energetic mechanical alloying was
also investigated earlier [129]. The milled NaAlH4 or Na3 AlH6
exhibited great improvement of the kinetics of absorption and
desorption. The addition of carbon in the milling process im-
proved their performance as well [120]. Mechanically alloyed
Na3 AlH6 exhibits faster kinetics than Na3 AlH6 obtained from
the decomposition of NaAlH4 [130]. Moreover, the hydrogen-
storage performance of NaAlH4 was found to be highly de-
pendent on the milling time which increases with time [117].
Consequently mechano-chemical synthesis method which in-
volves simply ball-milling of the appropriate reagents at high
energy, is applied to prepare Na3 AlH6 [114]. It can desorb the
same amount of hydrogen at 200 ◦ C within only 150 min and
 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1131

Table 3
Hydrogen absorption/desorption properties of sodium alanates

Material Method Temperature (C◦ ) Pressure (bar) Kinetics (min) Cycling stability Max Ref.
wt%
of H2

Na3 AlH6 Mechano-chemical Tdes : 200 Pdes : 1 tdes : 150 No data 2.50 [114]
synthesis
Na2 LiAlH6 BM Tabs : 211 Pabs : 45 tabs : 100 No data 2.50 [115]
NaAlH4 –2 mol% BM Tabs and Tdes : 125–165 Pabs and Pdes : 101–202 tabs : 60 5 cyc.: not 3.00 [116]
Ti(Obun )4 –2 mol% tdes : 180 stable
Zr(OPr i )4
NaAlH4 –4 mol% Ti BM Tabs : 120 Pabs : 120 tabs : 60 8 cyc.: not 3.30 [117]
Tdes : 150 Pdes : 1 tdes : 600 stable
NaAlH4 –2 mol% Ti BM Tdes : 25–160 Pabs : 20–120 tabs : 300–720 No data 3.80 [118]
Tabs : 25–193 Pdes : 1 tdes : 40
NaAlH4 –2 mol% Mixing Tabs : 120 Pabs and Pdes : 60–150 tabs : 1020 25 cyc.: not 4.00 [111]
(Ti(Obun )4 Tdes : 180–260 tdes : 120–300 stable [112]
NaAlH4 –2 mol% Mixing Tabs : 135–120 Pabs and Pdes : 150–130 tabs : 330 33 cyc.: not 4.00 [110]
Ti(Obun )4 Tdes : 180–160 tdes : 90 stable
NaAlH4 –2 mol% TiCl3 BM Tdes : 125–100 Pdes : 83–91 tdes : 20 5 cyc.: not stable 4.00 [116]
NaAlH4 –2 mol% Mixing Tdes : 200 Pdes : 1 No data 3 cyc.: stable 4.00 [119]
Zr(OPr)4 3 after second cyc.
NaAlH4 –2 mol% Mixing Tabs : 104 Pabs : 88 tabs : 1020 3 cyc.: stable 4.00 [113]
(Ti(Obun )4 ) after second cyc.
NaAlH4 Mechano-chemical Tabs and Tdes : 80–180 Pabs and Pdes : 76–91 tabs : 120–300 2 cyc.: not 5.00 [120]
synthesis tdes : 300 stable
NaAlH4 –2 mol% Mixing Tdes : 200 Pdes : 1 No data not stable 5.00 [121]
Ti(Obun )4 -C
NaAlH4 –2 mol% TiN BM Tabs : 104–170 Pabs : 115–140 tdes : 30–1200 25 cyc.: stable 5.00 [122]
after 17th cycle

without a catalyst, giving reaction rate about 10 times faster
than conventionally produced, non-catalyzed hydrides [114].
3.2. Lithium and potassium alanates
A survey of important studies on lithium-based hydrogen-
storage compounds are summarized in Table 4. It shows clearly
high capacities of stored hydrogen as weight percent material.
In theory, lithium alanates are very attractive for hydro-
gen storage, because of their high hydrogen content. The to-
tal hydrogen content is 10.5 and 11.2 wt% for LiAlH4 and
Li3 AlH6 , respectively. Unfortunately, LiAlH4 has an extremely
high equilibrium pressure of hydrogen, even at room temper-
ature. LiAlH4 is in fact an example of an unstable hydride,
which decomposes easily, but which cannot be re-hydrogenated
[114]. The desorption of LiAlH4 occurs in two steps:
3LiAlH4 → Li3 AlH6 + 2Al + 3H2 ,
Li3 AlH6 → 3LiH + Al + 23 H2 .
The hydrogen released in the two reactions shown, corre-
sponds to 5.3 wt% from the decomposition of LiAlH4 and
2.65 wt% from the decomposition of Li3 AlH6 at temperatures
between 160 and 200 ◦ C. After completion of the reactions,
2.65 wt% of the total hydrogen content in LiAlH4 remains
unreleased in form of LiH which can be desorbed only at
very high temperatures of above 680 ◦ C [114]. Therefore, the
commercialization of lithium-based compounds is hindered
by their slow kinetics and high temperature absorption and
desorption.
The reversible hydrogen decomposition of KAlH4 has been
studied previously [138]. The hydrogen capacity was above
3.5 wt% under 10 bar of hydrogen in a temperature range of
250–330 ◦ C, the reversible reaction smoothly proceeds without
any catalyst, which is different from the reactions of NaAlH4
and LiAlH4 [138].
3.3. Lithium nitrides
Lithium nitride is usually employed as an electrode, or as a
starting material for the synthesis of binary or ternary nitrides.
Although the temperature required to release the hydrogen
at usable pressures is too high for hydrogen-storage appli-
(5a) cations it was suggested that the metal–N–H system could
prove to be a promising route for reversible solid hydrogen
(5b) storage [45].
The idea of hydrogen storage in lithium compounds goes
back to 1910, when Dafert and Miklauz [139] reported the
reaction between Li3 N and H2 to Li3 NH4 . In fact Li3 NH4 has
been proved to be the product of the following reaction, which
was proposed by Ruff and Georges [140]:
Li3 N + 2H2 → LiNH2 + 2LiH. (6)
1132 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140

Table 4
Hydrogen absorption/desorption properties of Li-based hydrides

Material Method Temperature (◦ C) Pressure (bar) Kinetics (min) Cycling stability Max wt% Ref.
of H2

LaNi3 BH3 Arc melting Tabs : 25 Pabs : 4 tabs : 30 2 cyc.: not stable 0.84 [131]
Li2 NH Mixing Tabs and Tdes : 230–200 Pabs : 7 tabs : 10 15 cyc.: not 3.10 [132]
Pdes : 1 tdes : 300 stable
LiNH2 –LiH–1 mol% BM Tdes : 150–250 Pabs : 30 tabs : 30 3 cyc.: stable 5.00 [133]
TiCl3 Tabs : 180
Li2 O–Li3 N Partial oxidation Tabs : 180 Pabs : 7 tabs : 3 6 cyc.: stable 5.20 [134]
Li2 MgN2 H2 Mixing Tabs and Tdes : 180 Pabs : 90 tabs : 60 No data 5.50 [42]
Pdes : 1 tdes : 60
Li3 N Mixing Tabs : 50 Pabs : 0.5 tabs : 20 No data 6.00 [135]
Tdes : 240–270 Pdes : 1
Li2 NH Mixing Tabs and Tdes : 255–285 Pabs : 10 No data No data 6.50 [45]
Pdes : 1.5
Li3 BN2 H8 BM Tdes : 250–364 Pdes : 1 tdes : 228 No data 10.00 [136]
LiBH4 - 21 MgH2 –2 mol% BM Tabs and Tdes : 315–450 Pabs : 4.5–19 tabs : 240 3 cyc.: not 10.00 [137]
TiCl3 Pdes : 2–3 tabs : 240 stable

Consequently, Li3 N can theoretically store 10.4 wt% hydro-
gen. Li3 N has two plateaus in the P–C isotherm. Desorption
isotherms cannot return to the origin. Under P–C isotherm con-
ditions, about 55% of hydrogen can be desorbed at tempera-
tures above 230 ◦ C. More important for hydrogen storage, is
that this mixture could decompose to release hydrogen gas upon
heating, according to the following reaction:
LiNH2 + 2LiH → Li2 NH + LiH + H2 .
Hydrogen storage leads to the formation of LiNH2 and LiH.
Theoretically 7 wt% of hydrogen can be reversibly stored in
Li2 NH [45].
A critical potential issue regarding this N-based storage ma-
terial is the generation of NH3 , which consumes some H2 and
also poisons the downstream processes. Hu et al. [141] demon-
strated that NH3 produced via the decomposition of LiNH2 is
completely captured by LiH. This ultrafast reaction between
NH3 and LiH inhibits NH3 formation during the hydrogenation
of Li3 N [141].
Hu et al. [135] studied the temperature-programmed hydro-
genation and dehydrogenation of Li3 N and reported a reversible
hydrogen capacity of 6 wt%, within 240–270 ◦ C temperature
range. Another study of the same group was to investigate the
fast kinetics of LiO2 /Li3 N mixture for hydrogen storage [134].
They improved the activation characteristics of Li3 N with the
hydrogenation–dehydrogenation pretreatment, partially oxidiz-
ing the surface layer. They reported a maximum of 5.20 wt%
hydrogen capacity with very fast kinetics such as 3 min for
desorption.
A catalytic study of Ichikawa et al. [133] reported a 5.50 wt%
storage with high reaction rate after three cycles, with the uti-
lization of TiCl3 catalyst during ball-milling of the LiNH2 and
LiH mixture. Recently Hu et al. [132] reported a reversible hy-
drogen capacity of 3.10 wt%, that increases with the number
of cycles, due to improved porous structure of the material.
Another study on a different class of solid hydride has been
done by Pinkerton et al. [136], reporting an extraordinarily high
storage capacity of above 10 wt%, however, reversibility is lack-
ing. Although desorption conditions seem to be advantageous,
irreversibility stands as an important problem for use of these
materials to be utilized as storage medium. Authors reported
their attempts to rehydride the decomposition product by heat-
ing at 8 MPa but without success.
A proposed way for lowering the hydrogen desorption
temperatures of Li-based complex hydrides is partial cation
(7)
substitutions using different valence cations with larger elec-
tronegativities. It was predicted that the dehydriding reactions
of LiNH2 with partial Mg substitutions are useful as hydrogen-
storage materials for fuel–cell applications [142]. The starting
and ending temperatures for the hydrogen desorption reac-
tion from LiNH2 are lowered about 50 K by the partial cation
substitution of Li by Mg [143,144].
3.4. Lithium boro- and beryllium hydrides
The importance of boron for hydrogen-storage technologies
have been reported [145]. LiBH4 has a gravimetric hydrogen
density of 18 wt%. The compound was first synthesized by
Schlesinger and Brown [146] in an organic solvent. Accord-
ing to the work of Stasinevich and Egorenko [147] hydrogen
desorbs from LiBH4 at temperatures greater than 470 ◦ C.
Despite its great storage capacity, all attempts to synthesize
LiBH4 from the elements at elevated temperatures up to 650 ◦ C
and pressure of 150 bar H2 failed to date [108,148]. Moreover,
LiBH4 is an expensive compound [15].
It was found that the compound releases hydrogen in
different reaction steps and temperature regimes. The low
temperature desorption releases only a small amount (0.3 wt%)
of hydrogen. The high temperature phase releases up to
13.5 wt% of hydrogen. A total of 4.5 wt% of the hydrogen
remains as LiH in the decomposition product.
Vajo et al. [137] show that LiBH4 can be reversibly store
8–10 wt% hydrogen at temperatures of 315–400 ◦ C by addi-
tion of MgH2 including 2–3 mol% TiCl3 . Formation of MgB2
 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
stabilizes the dehydrogenated state and destabilizes the LiBH4
[137]. However, the kinetics is too slow with the absorption
time up to 6000 min hinder practical applications.
Besides alanates, nitrides and borohydrides, lithium–beryllium
hydrides are a new group of metal hydrides for hydrogen stor-
age. They show high reversible hydrogen capacity with more
than 8 wt% at 150 ◦ C. The reaction of hydride formation is
fully reversible. Since lithium and beryllium are the lightest
hydride-forming metals, reversible hydrogen capacity in these
complex compounds is higher than in any other known hy-
drides [149]. On the other hand, the Li3 Be2 H7 is a highly toxic
material [15].
4. Intermetallic compounds
Research on intermetallic compounds for hydrogen storage
was already attempted more than 20 years ago. The discovery
of hydrogen absorption by LaNi5 [150] and FeTi [151], opened
new possibilities for industrial developments. However, for on-
board storage, they remained at the stage of prototypes due
their weight penalty and low hydrogen-storage capacity [152].
The different families of intermetallic compounds classified
on the basis of their crystal structures, such as AB2 type (Laves
phase), AB5 type phases and Ti-based body centered cubic,
BCC, alloys are well known as hydrogen-storage materials.
Intermetallic compounds are often obtained by combining an
element forming a stable hydride with an element forming a
nonstable hydride. As for the metallic hydrides, the dissociative
chemisorption of hydrogen is followed by hydrogen diffusion
into the interstitial sites.
The hydriding properties of these compounds are summa-
rized in Tables 5 and 6. For practical applications at ambient
temperature and pressure, their low energy density per unit
weight is an important critical disadvantage. For instance,
the hydrogen capacity of the most popular LaNi5 -based al-
loys operating at moderate temperature does not exceed
1.4 wt%.
Among the AB5 type alloys, due to their low working tem-
perature and pressure, metal alloys containing high amounts of
LaNi5 have been studied as hydrogen-storage materials by var-
ious research groups around the world [176–180]. Some of the
studies were carried with pure compounds, while others stud-
ied blending of the material with various metals through melt-
ing or mechanical alloying techniques. Important results from
these studies are represented below.
The parent compound LaNi5 absorbs about 1.0 H/LaNi5
(1.5 wt%), however, its cost is relatively high and the plateau
pressure is low. The P–C diagram shows a flat plateau, low
hysteresis, but unfortunately the hydrogen capacity is de-
graded after a few cycles. Therefore, these materials are still
far from meeting the US DOE goal of 6.5 wt% reversible
hydrogen capacity. Due to their potential for commercial appli-
cations, researchers have been studying the effects of milling,
mechanical alloying or melting with other metals and surface
treatment techniques such as carbon monoxide treatment.
Table 6 presents the major outputs from a number of studies
on AB5 type compounds for hydrogen storage.
1133
The early studies on LaNi5 as hydrogen-storage material has
been reported by Aoyagi et al. [67]. The effect of ball-milling
on hydrogen absorption properties has been investigated, and
maximum hydrogen content has been reported as 0.25 wt%. It
is concluded that activation treatment is necessary for LaNi5
to be useful for hydrogen-storage applications. Kaplan et al.
[181] have investigated the hydrogen absorption in pure LaNi5
both theoretically and experimentally. The group reported that
LaNi5 has 1.28 wt% hydrogen-storage capacity for 8.3 min hy-
driding process. They characterized the hydriding process by
exothermic reaction between LaNi5 and H2 that leads to rapid
temperature increase. These supported the results from theoret-
ical calculations.
With different stoichiometric addition of other metals, LaNi5
compounds were shown to be enhanced for hydrogen-storage
by the works of Chen et al. [182], Corre et al. [175], and Lu et al.
[174]. They achieved hydrogen-storage capacities with differ-
ent stoichiometric LaNi5 samples such as 1, 1.44 and 1.32 wt%,
respectively. Chen et al. [182] applied chemical coating by cop-
per and achieved kinetics and cycling behavior during hydro-
genation /dehydrogenation process. By CO surface treatment,
1.44 wt% hydrogen capacity is achieved in LaNi5 . Lu et al.
[174] processed the LaNi5 using a twin roll process in order to
achieve uniform nanocrystalline structure with 1.32 wt% stor-
age capacity.
Apart from the above reported works, a few important stud-
ies in the literature are worth mentioning. Liu et al. [183], Wang
et al. [184], and Suda et al. [185] reported on the fluorination of
hydriding alloys and its effects on properties. The aim of these
experiments was to form a Ni-rich layer in order to improve
the initial activation and impurity tolerance. There are also
theoretical studies found in the literature, on LaNi5 utilization
for hydrogen storage, tank design and optimization. Kikkinides
et al. [186] showed the direct relation between hydrogen-
storage performance and optimization in LaNi5 systems.
Storage time could be improved by 60% through optimization.
The mechanism of hydrogen diffusion in LaNi3 BHx is inves-
tigated. The results suggested that hydrogen occupies sites co-
ordinated by lanthanum and nickel only, while the basal La–B
planes act as barriers to hydrogen diffusion along the hexag-
onal axis. Boron has an adverse effect on the hydrogen sorp-
tion properties of intermetallic compounds because it acts as
a barrier for hydrogen diffusion and favors localization of the
hydrogen atoms in the metal matrix away from the boron atom
sites [131].
The AB2 type compounds are derived from the Laves phases
crystal structures. The potential AB2 types are obtained with
Ti and Zr on the A site. The B elements are represented mainly
by different combinations of 3d atoms, V, Cr, Mn and Fe. The
hydrogen-storage capacity can reach up to 2 wt% in Laves phase
V–7.4%Zr–7.4%Ti–7.4%Ni [166]. The Laves phase series of
compounds has attracted large attention in the last decade due
to their good hydrogen-storage capacity. Most of Laves phases
show relatively high capacities faster kinetics, longer life and a
relatively low cost in comparison to the LaNi5 -related systems
[155]. However, their hydrides are too stable at room temper-
ature [187]. In general the AB2 type compounds seem to be
 1134
Table 5
Hydrogen absorption/desorption properties of intermetallic compounds

Material Method Temperature (◦ C) Pressure (bar) Kinetics (min) Cycling stability Max wt% Ref.
of H2

MgS BM Tabs : −196 Pabs : 50 No data No data 0.50 [153]

La0.90 Ce0.05 Nd0.04 Pr0.01 Ni4.63 Sn0.32 Melting Tabs and Tdes : 100, 25 Pabs : 5–10 tabs and tdes : 6.6 No data 0.95 [154]
Pdes : 0.24
Zr(Cr0.8 Mo0.2 )2 Induction melting Tabs : 120 Pabs : 30 No data No data 0.99 [155]
Ml0:85 Ca0:15 Ni5 RF melting Tdes : 25 Pdes : 10 tdes : 60 100 cyc.: stable 1.10 [156]
LaNi4.8 Sn0.2 Arc melting Tdes and Tabs : 80 Pdes : 3–4 No data 1000 cyc.: stable 1.16 [157]
La0.55 Y0.45 Ni5 Induction melting Tdes : −20 Pdes : 3.5 No data 5 cyc.: stable 1.30 [158]
Ti0.9 Zr0.15 Mn1.6 Cr0.2 V0.2 RF melting Tdes : 25 Pdes : 10 tdes : 60 100 cyc.: stable 1.30 [156]
MmNi4.6 Al0.4 Melting Tabs and Tdes : 25 Pdes : 25 tdes : 5 11 cyc.: stable after ninth cycle 1.30 [159]
MmNi4.6 Fe0.4 Melting Tabs and Tdes : 25 Pabs : 35 tabs : 15 11 cyc.: stable after ninth cycle 1.44 [159]
Ml0.75 Ca0.25 Ni5 RF levitation melting Tabs : 20 Pabs : 100 No data No data 1.45 [160]
Pdes : 6.8
80 wt% TiCr1.1 V0.9 –20 wt% Melting + BM Tabs and Tdes : 30 Pabs : 17 No data No data 1.50 [161]
LaNi5 Pdes : 0.5
Ti0.97 Zr0.03 Cr1.6 Mn0.4 RF levitation melting Tabs : 20 Pabs : 100 No data No data 1.55 [160]
Pdes : 81
La0.7 Mg0.3 Ni2.65 Mn0.1 Co0.90 Melting Tabs and Tdes : 30 Pabs : 5 No data No data 1.56 [162]
Pdes : 0.33
Zr0.75 Ti0.25 Cr1.5 Ni0.5 Arc melting Tabs : 40 Pabs : 47 No data No data 1.75 [163]
Ti1.1 CrMn Arc melting Tabs and Tdes : 23 Pabs : 33 tabs : 1 1000 cyc.: stable 1.80 [164]
Pdes : 1 tdes : 5
FeTi BM Tabs : 25 Pabs : 100 No data No data 1.92 [165]
V–7.4%Zr–7.4%Ti–7.4%Ni Arc melting Tabs : 40 Pabs : 10 No data 10 cyc.: not stable 2.00 [166]
Pdes : 1
V0.375 Ti0.25 Cr0.30 Mn0.075 Arc melting Tabs and Tdes : 30 Pabs : 50 No data No data 2.20 [167]
Pdes : 0.2
Ti45 Zr38 Ni17 BM Tabs : 300 Pabs : 80 tabs : 1200 No data 2.23 [168]
Quasicrystal powders Tdes : 427
Ti–V–Cr Arc melting Tabs and Tdes : 40 Pabs : 100 No data No data 2.80 [169]
Ti–10Cr–18Mn–27V–5Fe Magnetic levitation melting Tabs : 60 Pabs : 30 tabs : 8.3 No data 3.01 [170]
Pdes : 1
B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140

Ti–10Cr–18Mn–32V Magnetic levitation melting Tabs : 60 Pabs : 30 tabs : 8.3 No data 3.36 [170]
Pdes : 1
TiCr1.1 V0.9 Melting + BM Tabs and Tdes : 30 Pabs : 17 No data No data 3.50 [161]
Pdes : 0.5
Ti43.5 V49 Fe7.5 Arc melting Tabs : −20 Pabs : 100 tabs : 20 50 cyc.:stable 3.90 [171]
Tdes : 300 Pdes : 10
Ti–V–Cr–Mn Magnetic levitation melting Tdes : 247–472 Pabs : 30 No data No data 3.98 [172]
Pdes : 0.03
La1.8 Ca0.2 Mg14 N13 BM Tabs and Tdes : 27–327 Pabs : 40 tabs : 15 6 cyc.: not stable 5.00 [173]
Pdes : 1 tdes : 10
 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
Table 6
Hydrogen absorption/desorption properties of LaNi5 compounds
Material Method Temperature (◦ C)
LaNi5 BM Tabs : 20
La0.59 Ce0.29 Pr0.03 Ni4 Co0.45 Mn0.45 Al0.3 Twin-rolling Tabs : 60
La0.9 Ce0.1 Ni5 CO surface Tabs : 0–100
treatment
Tdes : 25
LaNi5 CO surface Tabs : 0–100
treatment
Tdes : 25
more sensitive to gaseous impurities than the AB5 type com-
pounds. Thus, a small amount of oxygen can be a poison for
the AB2 s, while, for the AB5 s, it acts as a reactant, reducing the
storage capacity slightly. CO is a poison for both types of com-
pounds, although capacity recovery is possible by recycling in
pure hydrogen [188].
Hydrogen absorption of FeTi powders has previously been
extensively studied. FeTi is a well-known hydrogen-storage
compound with a total hydrogen capacity of around 1.90 wt%
with inexpensive elements. Hydrogen capacity of FeTi can be
accomplished to 1.90 wt% by the catalytic effect of 1 wt% Pd
addition [165]. However, the activation process of FeTi is trou-
blesome due to the formation of titanium oxide layer. Both
high-pressure and high temperature are required to achieve a
reproducible absorption/desorption of the maximum amount of
hydrogen in the compound [151,187].
New BCC solid solution alloys have been reported to ab-
sorb more hydrogen than the conventional intermetallic com-
pounds. In recent years, study of Ti-based BCC phase alloys
has been studied in several laboratories because of their remark-
able hydrogen capacities. However, the high cost is one of the
critical drawbacks limiting their successful practical applica-
tions. Ti–10Cr–18Mn–27V–5Fe and Ti–10Cr–18Mn–32V has
hydrogen-storage capacities of 3.01 and 3.36 wt%, respectively
[170]. Increasing the V content is effective in accelerating hy-
drogen absorption, enhancing the hydrogen absorption capacity
and flattening the hydrogen desorption plateau, while decreas-
ing hydrogen desorption plateau pressure. The maximum and
effective hydrogen-storage capacities of Ti–V–Cr–Mn alloys
are 3.98 and 2.51 wt%, respectively [172].
It is well known that vanadium is expensive; therefore, de-
creasing of the vanadium content is another goal of the investi-
gations. In Ti–V–Cr–Mn compounds, increasing the Cr content
and the addition of Mn is necessary to increase the effective hy-
drogen capacity by increasing the plateau pressure, but also to
decrease costs by decreasing the vanadium content. The BCC
phase solid solution of V0.375 Ti0.25 Cr 0.30 Mn0.075 exhibited an
effective hydrogen capacity of 2.20 wt% [167].
In order to improve the hydrogen-storage properties and re-
duce the cost of Ti–V-based BCC alloys, the effect of Fe substi-
tution in Ti–10Cr–18Mn–32V alloy is also investigated [170].
It was reported that Fe addition increases the activation perfor-
1135
Pressure (bar) Kinetics (min) Cycling stability Max wt% Ref.
of H2
Pabs : 20 tabs : 1.6 8 cyc.: not stable 0.25 [67]
Pabs : 10 No data No data 1.27 [174]
Pdes : 0.6
Pabs : 50 tdes : 1.8 20 cyc.: stable 1.40 [175]
after fifth cycle
Pabs : 50 tdes : 13.6 20 cyc.: stable 1.44 [175]
after fifth cycle
mance, hydrogen absorption–desorption plateau pressure, hy-
drogen desorption capacity and reduce the hysteresis of hydro-
gen absorption–desorption plateau, and the cost of alloy [170].
The quasicrystals have a new type of translational long-range
order, display non-crystallographic rotational symmetry. They
contain high amounts of interstitial sites. The quasicrystalline
Ti45 Zr 38 Ni17 has 2.23 wt% storage capacity [168]. The sorp-
tion of hydrogen between the layers of the multilayered wall
of nanotubular TiO2 was studied in the temperature range of
195–200 ◦ C and at pressures of up to 6 bars. Hydrogen can in-
tercalate between layers in the walls of TiO2 nanotube [189].
5. Conclusion
Hydrogen storage is a key issue in the success and realiza-
tion of hydrogen technology and economy. According to US
DOE, the hydrogen-storage capacity target for commercializa-
tion is 6.5 wt% at the decomposition temperature between 60
and 120 ◦ C with high cycle life. Although pure water contains
11.1 wt% of hydrogen, its decomposition requires much ther-
mal, electric, or chemical energy [15].
Since the conventional hydrogen fuel storage methods of
pressurized H2 gas and cryogenic liquid H2 pose safety and per-
meation problems along with high cost, they do not meet future
on-board applications goals set for hydrogen economy. Solid
state hydrogen fuel storage either absorption in the interstices
of metals and metallic alloys or adsorption on high surface area
materials such as activated carbons gain the attention for pos-
sible future hydrogen applications. The present article reviews
the hydrogen-storage materials for transport applications which
require research into further aspects of tank technology, heat
management and solid fuel recycling. The work is carried out
in an attempt to facilitate prospectus material choice for further
tank design aiming at on-board vehicle applications.
Hydrogen can be stored in metal hydrides under moderate
temperature and pressure. Metal hydrides are the promising
candidates due to their safety advantage with high volume-
efficient storage capacity for on-board applications. Intensive
research has been recently conducted on the metal hydrides for
improving adsorption/desorption properties based on hydrogen-
storage capacity, kinetics, thermal properties, toxicity, cycling
behavior and cost.
1136 B. Sakintuna et al. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
Group of Mg-based hydrides is a promising candidate for
competitive mobile hydride storage with the reversible hydro-
gen capacity of up to 7.6 wt%. However, slow kinetics and high
hydrogen desorption temperatures up to about 300 ◦ C reduce
the efficiency and applicability in vehicles. Although much ef-
fort has been devoted to those materials in order to decrease
their decomposition temperature, enhance the kinetics and cy-
cle life by using appropriate catalysts and production method
of ball-milling, further research is needed.
The complex hydrides released hydrogen by the step reac-
tions unlike the metallic hydrides. Although the storage ca-
pacities of complex hydrides are theoretically high, there is a
big difference between the theoretical and the presently practi-
cal attainable hydrogen capacities. Repeated hydrogenation cy-
cles need to be applied for the potential applications to ensure
the reversibility of these materials. Moreover, the slow kinetics
problem is a significant obstacle for practical on-board applica-
tions. The intermetallic compounds do not satisfy the require-
ments for mobile storage for the reason that their low storage
capacities up to 2 wt% for available use and along with high
costs. An alternative application may be seen in effective use
as thermodynamic devices [188].
There is no perfect choice of hydrogen store material to
meet the set US DOE goals for transport applications. Although
some results are encouraging, such as improved kinetics and
lower decomposition temperatures for metal hydrides, further
research is needed to develop materials satisfying the needs for
technical applications. In the light of the achievements, there is
high potential in developing better hydride materials with high
reversible hydrogen capacity at ambient temperatures. In ad-
dition, technological improvements in vehicle design and sys-
tem integration along with cost efficiency will determine the
on-board applicability of the selected material [2]. The success
and realization of hydrogen economy using hydrogen stored
solid fuel technology will be dependent on the meeting of
above goals.
Acknowledgments
Support for this work was provided by the EU FP6 RTN
Project HyTRAIN; Hydrogen Storage Research Training Net-
work. Figs. 1–5 reprinted from indicated references with kind
permission of the Elsevier and International Journal of Hydro-
gen Energy are acknowledged.
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