i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1

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Review Article

Recent advances in catalyst-enhanced LiAlH4 for

solid-state hydrogen storage: A review

N.A. Sazelee, M. Ismail*

Energy Storage Research Group, Faculty of Ocean Engineering Technology and Informatics, Universiti Malaysia
Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia

highlights graphical abstract

Recent advances in catalyst-

enhanced LiAlH4 is reviewed.

Roles of catalyst in catalyst-
enhanced LiAlH4 is highlighted.

The remaining challenges and the
future prospect of LiAlH4 is
discussed.

article info abstract

Article history: LiAlH4 is regarded as a potential material for solid-state hydrogen storage because of its
Received 3 November 2020 high hydrogen content (10.5 wt%). However, its high decomposition temperature, slow
Received in revised form dehydrogenation kinetics and irreversibility under moderate condition hamper its wider
15 December 2020 applications. Mechanical milling treatment and doping with a catalyst or additive has
Accepted 28 December 2020 drawn significant ways to improve hydrogen storage properties of LiAlH4. Microstructure or
Available online 22 January 2021 nanostructure materials were developed by using a ball milling technique and doping with
various types of catalysts or additives which had dramatically improved the efficiency of
Keywords: LiAlH4. However, the state-of-the-art technologies is still far from meeting the expected
Hydrogen energy goal for the applications. In this paper, the overview of the recent advances in catalyst-
Hydrogen storage enhanced LiAlH4 for solid-state hydrogen storage is detailed. The remaining challenges
Solid-state storage and the future prospect of LiAlH4ecatalyst system is also discussed. This paper is the first
Lithium alanates systematic review that focuses on catalyst-enhanced LiAlH4 for solid-state hydrogen
Catalyst storage.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail addresses: mohammadismail@umt.edu.my, mi300@uowmail.edu.au (M. Ismail).
https://doi.org/10.1016/j.ijhydene.2020.12.208
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
9124 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9124
Properties of LiAlH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9125
Improvement of LiAlH4 properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9127
Milling process and surface modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9127
Doping with catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9128
Transition metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9129
Metal halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9129
Metal oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9131
Metal hydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9133
Metal carbide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9134
Carbon-based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9135
Challenges and prospects of LiAlH4 as a hydrogen storage material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9135
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9136
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9136
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9136
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9136

medium [14e18]. In fact, hydrogen is also a carbon-free

Introduction
Year by year, the population had grown dramatically.
Currently, the world population is increasing at a rate of
200,000 inhabitants per day, which stands at approximately
6.5 billion and will soon range from 8 to 10 billion [1,2]. As
populations rise with the expectation of a decent living con-
dition, global energy consumption will continue to increase,
an increasing share of which is attributable to developed na-
tions [3]. In response to global warming and environmental
pollution due to the continued usage of fossil fuels, alternative
sources of clean energy have been developed. The modern
economy requires energy to produce its goods. To search for a
better energy source that can replace fossil fuels is a signifi-
cant challenge for human beings. Carbon dioxide emission is
one of the main causes of environmental pollutants, arising
mainly from fossil fuel combustion. The increasing environ-
mental emissions and demand for electricity have called for
the use of renewable energy. The main aim is to pursue
renewable energy and a viable fossil fuel alternative, which is
clearly very challenging. Consequently, a solution is required
to decide the path of energy in the growth.
Biomass as one of the carbon dioxide reducing source of
energy [4], however major disadvantages of biomass energy
are damage of natural ecosystems, high investment cost and
insecurity of biomass feedstock supply [5]. Hydrogen is the
largest abundant component on the earth and was regarded
as a secondary form of energy since it comes from natural
resources and bioresources [6e9]. This allows hydrogen to
provide a long-term alternative that can lead to a difference in
the supply of automotive fuel [10e13]. Hydrogen can be
defined as an energy carrier that has a high capacity for
effective power in applications such as stationary, portable
and transport. Additionally, besides being naturally clean,
hydrogen has interesting characteristics as an energy storage
renewable energy that has a weight-based heating value
that is two times that of fuel [19,20]. Therefore, research have
reported that hydrogen can be a promising energy carrier
[21e23]. Since the global crisis in 1974, the concept of using
hydrogen as an energy carrier has been worth noting [24].
The cost for hydrogen technologies need to be calculated
for future. Fig. 1 below shows the cost categories including the
generation, distribution and usage cost [25]. The capital in-
vestment cost consists of the construction, equipment cost
and preparation for hydrogen technologies. The cost of
running includes raw materials cost and the other variable
cost of operation. The disposal cost consists of the waste
treatment. Finally, any costs not included in the previously
mentioned cost categories that may have potential effects on
the analysis are taken into account in the other costs.
However, currently, hydrogen energy is facing a big chal-
lenge in terms of storage. Because of the high demands on the
efficiency of candidate materials, hydrogen storage has long
been known as a challenging concern. Hydrogen can be stored
in three separate forms, namely, compressed gas, liquid state
and solid-state [26e31]. Among the three forms, compressed
gas hydrogen storage has the most advanced technology and
is commonly used in a range of practical applications. A
typical technique for storing hydrogen in a compressed gas is
to compress the gas in gas cylinders with a maximum storage
pressure of 20 MPa. Nowadays, however, hydrogen automo-
biles worked at 35e67 MPa [32,33]. Additionally, preservation
in a gaseous form has some disadvantages such as high cost
and heavy maintenance. The hydrogen compressed tank
should be highly resistant, lightweight and strong [34]. The
design of the tank gas is usually cylindrical and made of fiber
filament winding composite as shown in Fig. 2.
Liquid hydrogen is commonly used and is stored in tanks
with different shapes and sizes. In the future, liquid hydrogen
may be transported in large amount, necessitating a large
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1
Fig. 1 e Major cost categories for life cycle costing analysis [25].
Fig. 2 e Schematic diagram of a pressurized hydrogen
storage tank [151] .
tank to store it. The tanks are typically cylindrical or rectan-
gular. The cylindrical tank has a larger surface area than a
spherical tank has. However, the pressure inside the cylin-
drical tank is high but not equally distributed. Therefore, a
larger and thicker wall is required [36]. The liquid hydrogen
should be maintained at around 20 K (253  C); hence, because
of the significant temperature differential between the
ambient and liquid hydrogen, the heat leakage in such tanks
may occur. Also, liquid hydrogen can only be stored in open
systems because of the low critical hydrogen temperature
(33 K) [37]. Fig. 3 shows one of the examples of liquid hydrogen
tanks. The high low-pressure density of liquid hydrogen
(70.8 g/L for saturated liquid at 1 bar) enabled the cryogenic
liquid to become more compact than compressed hydrogen
cylinders [38]. Energy consumption is also high during lique-
faction, i.e. close to 30% of the total hydrogen energy in
practical engineering applications [39].
The main advantage of store hydrogen in solid-state form
is that a large quantity of hydrogen can be stored in a
comparatively small volume compared with in the com-
pressed gas and liquid-state forms [41]. Additionally, the
preservation of solid-state hydrogen storage is one of the best
9125
and most economical options in onboard applications [42e46].
The use of solid absorber is relatively safe and enables a
higher volumetric capacity compared with that using com-
pressed gas and liquid-state forms. There are two common
types of solid-state hydrogen storage: physisorption and
chemisorption. The examples of physisorption materials
include metaleorganic frameworks (MOF), zeolites and
carbon-based materials, such as graphite, carbon nanotubes
(CNTs) and graphene [47,48]. Meanwhile metal hydrides and
complex hydrides are the examples of chemisorption mate-
rials [49e53]. Compared with physisorption, chemisorption is
regarded as a promising material to store hydrogen in a solid-
state form, owing to its high hydrogen capacity. For example,
magnesium hydride (MgH2) will release approximately 7.6 wt
% of hydrogen when heated up to 400  C, and lithium alanate
(LiAlH4) will desorb approximately 7.9 wt% of hydrogen when
heated up to 350  C. Fig. 4 illustrates the solid-state hydrogen
storage for metal hydride. Hydrogen is first ‘sorbed’ into the
material and then released under controlled heating of solid.
Fig. 4 shows that the hydrogen gases were diffused into the
metal host and formed metal hydride.
However, high decomposition temperature, slow sorption
kinetics and poor reversible release/uptake hydrogen under
moderate conditions hamper the applications of chemisorp-
tion materials. Hence, it is important to have materials that
can be recharged rapidly with hydrogen and released
hydrogen in a controlled manner under moderate tempera-
ture and pressure conditions [55]. Thus, appropriate materials
must be sought to satisfy the specifications for large-scale
applications. This review reveals that researchers are work-
ing on solving this task.
Properties of LiAlH4
In this review, alanates or complex aluminohydrides can be
stated as a family of compounds that comprise hydrogen and
aluminium. Normally, Al will be at the center of the tetrahe-
dron. Examples of alanates include LiAlH4, NaAlH4, KAlH4,
9126 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1

Fig. 3 e Schematic diagram of a cryogenic hydrogen tank [40].

Fig. 4 e Schematic description of hydrogen storage on metal hydrides [54].

Mg(AlH4)2 and Ca(AlH4)2 [56]. Table 1 shows the material
properties of alanates.
Since the work of Bogdanovic and Schwickardi [35] in 1997,
demonstrating the reversible hydrogenation of Ti, which
improved the hydrogen storage performance of NaAlH4, ala-
nates have gained significant attention because of their high
hydrogen storage ability. In the last few years, the importance
of alanates in hydrogen storage has increased rapidly. Among
the group of alanates, LiAlH4 has attracted significant interest
because of its higher capacity of 10.5 wt% hydrogen and low
cost [59,60]. Fig. 5 shows that the crystal structure of LiAlH4
stands out.
Eqs. (1)e(3) describe that LiAlH4 decomposes in three re-
action steps. Theoretically, the first reaction step begins at
150  C and releases ~5.3 wt% of hydrogen [61e63]:
3LiAlH4 / Li3AlH6 þ 2Al þ 3H2 [1]

Table 1 e Properties of complex hydrides [57,58]. The second reaction step starts at 180  C and desorbs
~2.6 wt% of hydrogen:
Materials Molecular Hydrogen Decomposition
weight (g/ capacity temperature ( C)
mol) (wt.%) Li3AlH6 / 3LiH þ Al þ 3/2H2 [2]
LiAlH4 37.95 10.54 160
The third reaction step begins at >350  C and releases
NaAlH4 53.97 7.41 210
KAlH4 70.08 5.71 300 ~2.6 wt% of hydrogen.
Mg(AlH4)2 86.3 9.27 110
Ca(AlH4)2 102.04 7.84 130 3LiH þ 3Al / 3LiAl þ 3/2H2 [3]
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1
Fig. 5 e Crystal structure of LiAlH4 [58].
Despite their high ability to store hydrogen, that is, 10.5 wt
% of hydrogen, substantial work needs to be done on LiAlH4
for onboard hydrogen storage. Additionally, the beginning
temperature of decomposition for LiAlH4 is lower than those
of the other alanates. Unfortunately, certain issues such as
weak reversibility and sluggish desorption kinetics limit the
widespread use of LiAlH4. These are the key problems that
make LiAlH4 impractical for applications for hydrogen storage
[64,65]. When LiAlH4 was heated at >350  C, it decomposed
into LiAl and hydrogen. Clearly, it is a high desorption tem-
perature for commercial applications.
Improvement of LiAlH4 properties
Many attempts have been made to overcome the disadvan-
tages of LiAlH4 properties (slow sorption kinetics and poor
reversibility) such as mechanical treatment by using ball
milling and doping with catalysts or additives.
Milling process and surface modifications
Ball-milling methods were commonly used by many re-
searchers because of the evidence that milling process will
decrease the particle size of the materials. Processes of milling
contribute to enhancing the de/rehydrogenation kinetics of an
alloy and metal hydrides [49,66,67]. It is a simple but effective
process that is typically used for mechanical alloying pur-
poses or to create fine powders with a lot of fresh surfaces
(even nanostructures can be produced). One of the most
common mills is the planetary ball mill where at one time, a
few hundred grams of the powder that can be milled. They are
arranged on a revolving support disk and spin through a
special drive mechanism along their axes. The centrifugal
force created by the vials revolving along their axis and
created by the spinning support disk. This also operates on the
vial’s contents, the substance to be ground and the grinding
9127
balls. The centrifugal forces operate alternately in opposite
and same directions, regardless of the vials and the support-
ing disk spinning in opposite directions. It causes the grinding
balls to travel down the inner wall of the flap, followed by the
ground material and the grinding balls to lift and move easily
through the inner chamber of the flap to clash with the
opposing wall [68]. Fig. 6 display the schematic diagram of the
ball movement.
Mechanical milling treatment increases the surface area
and creates microstructure or nanostructure materials, and,
as a result of the milling effects, it produces defects on the
surface or inside the surface [70,71]. El-Eskandarany et al. [72]
also disclosed the use of a ball milling technique to synthesize
nanocrystalline MgH2 powders. In addition, Fatay et al. [73]
showed that commercial MgH2 powders exhibit particles with
an average of 40e50 mm. The average size of the powder’s
particles decreased significantly down to approximately 1 mm
after the commercial MgH2 was milled for 120 min. Andreason
and his co-workers [74] also investigated the impact of the ball
milling method of LiAlH4. Different milling times of LiAlH4 on
the desorption kinetics are expressed by isothermal dehy-
drogenation kinetic curves for all ball milled samples. In their
study, LiAlH4 was milled for 1, 2, 4 and 6 h. Each sample
showed different results for the kinetics curves of
dehydrogenation.
The smaller particle size could boost the properties of
hydrogen storage of the LiAlH4 by reducing the diffusion
length. Varin and Zbroniec [75] reported the distribution of the
morphology and particle size of commercial LiAlH4 powder, as
displayed in Fig. 7. The figure shows that individual LiAlH4
particles have a “blocky” form for the morphology. Further
analysis shows that after measuring approximately 1200
particles, the equivalent circle diameter obtained for as-
received LiAlH4 is 9.9 ± 5.2 mm.
Additionally, Varin and Zbroniec [75] have elucidated that
the particle sizes are getting smaller after LiAlH4 was milling
under high energy impact for 2 h, as shown in Fig. 8(a).
Fig. 6 e Schematic diagram of the ball motion inside the
planetary ball mill [69].
9128 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1

Fig. 7 e (a) Scanning electron backscatter micrograph of the as received LiAlH4 particles and (b) Configuration of the as
received LiAlH4 particle distribution histogram using the extreme probability distribution function [75].

Meanwhile, Fig. 8(b) showed an equal circle diameter of
2.8 ± 2.3 mm after LiAlH4 was milling. This result proved that
the ball milling technique significantly reduced the particle
size of LiAlH4. More hydrogen would result in a decrease in
particle size, greater surface area and more grain boundaries
[76,77]. Furthermore, Sulaiman et al. [78] reported that the
findings of surface morphology showed a good dehydriding
performance after ball milling due to reduced particle size and
that the process of producing small crystallite sizes caused a
high surface defect density and decreased grain boundaries.
Ares et al. [71] explored the thermal stability of as-received
and as-milled LiAlH4. This work further elucidated the influ-
ence of parameters including crystallite size and particle size
on the temperature of the LiAlH4 decomposition. Further-
more, for the first decomposition reaction, the activation en-
ergy of as-milled LiAlH4 is lower than that of as-received
LiAlH4. Based on the review above, it can be inferred that
smaller particle sizes greatly increase the kinetics of desorp-
tion and the activation energy of LiAlH4. Interestingly, the
influence of milling time also gives a different result on the
particle morphology of LiAlH4. From the result obtained, the
particles are refined after LiAlH4 has been milled below 1.5 h.
Conversely, the 30 min-milled sample also reveals very large
particles (Dp ¼ 80 ± 40 mm). The 1.5 h-milled sample now
shows a smaller, more homogeneous particle size distribution
(Dp ¼ 30 ± 15 mm). However, smaller particles tend to
agglomerate to the end of this stage. When the milling time
rises (>1.5 h), the LiAlH4 particles agglomerate more and the
particle size is not reduced any further (Dp ¼ 35 ± 10 mm).
Doping with catalyst
As discussed earlier, the attempt to resolve the obstacles for
LiAlH4 as a material for solid-state hydrogen storage was
made with compound modifications, which include particle
size reduction using the ball milling technique. In this tech-
nique, the particle sizes of the sample become smaller,
creating a lot of fresh surface areas. Additionally, the samples
have short distance grain boundaries and provided a fast
diffusion path, speeding up the diffusion of the hydrogen
atom into the materials [79,80]. Additionally, doping with
catalysts or additives is well known to be a significant method
for enhancing the hydrogen storage properties of metal/
complex hydrides [81e87]. In this paper, we have reviewed six
different groups of catalysts or additives for the enhancement
of hydrogen storage properties of LiAlH4, namely, transition

Fig. 8 e (a) LiAlH4 secondary electron micrograph scanning with R132 after ball milling for 2 h in high energy mode IMP68
and (b) Particle size Equivalent Circle Diameter distribution for milled powder [75].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1 9129

metal, metal halide, metal oxide, metal hydride, metal carbide

Table 3 e Temperature ( C) and dehydrogenation amount
and carbon-based materials.
(wt.%) of doped samples in the first (R1) and second (R2)
steps [89].
Transition metal
Parameters LiAlH4 LiAlH4 þ 5 mol LiAlH4 þ 5 mol
Over a decade ago, several experiments have been conducted
% Ti % Ni
focusing on the impact of transition metal on LiAlH4. Xueping
1st decomposition ( C) 148 135 145
and co-workers [88] studied the impact of Fe and Ti additives
2nd decomposition ( C) 176 175 184
on hydrogen released by LiAlH4. Since LiAlH4 was doped with Hydrogen amount for 4.0 3.5 3.3
Ti and Fe, the temperature-programmed desorption (TPD) R1 (wt.%)
curve has changed dramatically. After the addition of transi- Hydrogen amount for 2.0 1.6 1.8
tion metal catalyst (Ti and Fe), the initial desorption temper- R2 (wt.%)
ature for LiAlH4 was lowered by 25  C and 35  C for that doped Total hydrogen release 6.0 5.1 5.1
(wt.%)
with Ti and Fe catalysts, respectively. However, for the LiAlH4
þ 5 mol% Fe and LiAlH4 þ 5 mol% Ti, the amount of hydrogen
released was reduced by 0.47 and 0.7 wt%, respectively, as
the activation energy of LiAlH4 was substantially reduced after
shown in Table 2.
Fe catalyst was applied although the mode of milling and the
Xueping and Shenglin [89] also revealed that the TPD
Fe additives were different. It is apparent that each mode of
curves of LiAlH4 improved, but the amount of hydrogen
milling or energy results in the expansion of the volume of
released was reduced after the addition of 5 mol% Ti and 5 mol
crystals, whose magnitude depends on the friction force, the
% Ni. The decomposition temperature of LiAlH4 þ 5 mol% Ti
additive shape and the particle size. A significant finding is
and LiAlH4 þ 5 mol% Fe was lowered by 13  C and 3  C for the
that LiAlH4/nanometric Fe high energy results in hydrogen
first decomposition reaction step (as in Eq. (1)). However, the
desorption during milling as the volumetric lattice expansion
total hydrogen desorption capacity was reduced after the
increases more than 1%. Fully dehydrogenated product
addition of a transition metal catalyst. The same phenomena
(LiAlH4 5 wt% nanometric Fe) was partly rehydrogenated for
were similar to the present study [90]. This occurs because of
24 h at 160  C up to 0.5 wt% hydrogen under 100 bars. However,
the dead weight of the catalyst. Table 3 reveals the dehydro-
the mechanisms of rehydrogenation are not yet optimized.
genation amount and temperature for the doped and undoped
The addition of Fe catalyst thus greatly enhanced the dehy-
samples.
drogenation kinetics of LiAlH4.
Although several studies about how the Ti catalyst will
boost LiAlH4 dehydrogenation abilities have been conducted,
Metal halides
the exact function the Ti plays is still yet to be addressed.
Studies on the use of catalysts such as metal halides to lower
Next, Ti-doped LiAlH4 was studied by Amama et al. [91]. Fig. 9
LiAlH4 desorption temperature and to enhance the kinetic
shows the schematic transformations of Ti-doped LiAlH4.
performance of LiAlH4 can be found in the literatures [93e103].
They believed that reducing Ti and Li surface segregation
Recently, Cao et al. [93] investigated the dehydrogenation
work together during the milling process to destabilize LiAlH4
behaviours LiAlH4 chemically mixed with ScCl3 and found
is primarily responsible for enhancing the dehydrogenation of
that the hydrogen storage performance of LiAlH4 was signifi-
LiAlH4.
cantly improved. They disclosed that as-received LiAlH4, as-
Varin and Parviz [92] have also shown that adding transi-
milled LiAlH4 and x mol% of ScCl3-doped LiAlH4 (where x is
tion metal (Fe) has a beneficial influence on LiAlH4 dehydro-
1, 2, 5 and 10) displayed a two-stage temperature character-
genation. Ironically, they have studied the impacts of the
istic from 30  C to 300  C. The first stage corresponds to the
nanometric and micrometric iron (Fe) additions on the me-
LiAlH4 decomposition, and the second stage is associated with
chanical and thermal dehydrogenation of LiAlH4. Table 4
Li3AlH6 decomposition. Since ScCl3 is applied, the tempera-
shows the micrometric and nanometric Fe activation energy
ture of the onset of decomposition falls to 90  C, which is
measured using different energy modes. The table shows that
reduced by 54  C. SEM images also revealed that the particle
sizes of LiAlH4 were decreased after the addition of ScCl3. The
particle size refinement produces a larger surface area, high
Table 2 e Temperature ( C) and dehydrogenation amount defect density as well as ample grain boundaries, which will
(wt.%) of hydrogen released from LiAlH4, Fe-doped LiAlH4 reduce the diffusion distances and maximize the interfaces to
and Ti-doped LiAlH4 in the first (R1) and second (R2) steps the reaction, thereby promoting the decomposition of LiAlH4.
[88]. Furthermore, the in situ formed compound ScH2 formulation
Parameters LiAlH4 5 mol% 5 mol% acts as a real catalyst for hydrogen desorption while
Ti þ LiAlH4 Fe þ LiAlH4 increasing the ability of LiAlH4. In 2007, Ares Fernandez and
Temperature start ( C) 150 125 115 colleagues [94] reported the enhancement of LiAlH4 storage
Temperature end ( C) 245 250 235 properties with three metal halides, namely, AlCl3, VCl3 and
Hydrogen amount for R1 3.89 3.59 4.00 VBr3. LiAlH4 þ VCl3, LiAlH4 þ VBr3 and LiAlH4 þ AlCl3 show two
(wt.%)
decomposition steps as occurred in as-milled LiAlH4, shown in
Hydrogen amount for R2 2.18 1.78 1.60
Eqs. (1) and (2). Furthermore, compared with that of as-milled
(wt.%)
Total hydrogen 6.07 5.37 5.60 LiAlH4, all samples milled with these metal halide catalysts
desorption (wt.%) had decreased reaction decomposition. These metal halides
9130 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1

Fig. 9 e The inferior dehydrogenation properties found in LiAlH4 samples doped with Ti metal are due to the absence of both
phenomena, i.e., Ti reduction and Li surface segregation [91].

weaker and wider than those of as-received LiAlH4 (without

Table 4 e Apparent dehydrogenation activation energies milling). It also indicates that LiAlH4 has already partially
for LiAlH4 with the nanometric -Fe additive and
decomposed into Li3AlH6 and Al after the samples were milled
micrometric-Fe additive ball milled under low energy
(LES6) and high energy (IMP68) milling modes [92]. for 30 min in the presence of 4 mol% of TiF3. Furthermore,
dehydrogenation started at 80  C for LiAlH4 þ 4 mol% of TiF3
Milling mode/additives Apparent activation
milled for 30 min. As the milling time was increased up to 18 h,
energy ± standard
error (kJ/mol) dehydrogenation started at 60  C. Furthermore, as the milling
time was increased, the crystallite sizes became smaller.
Stage 1 Stage 2
Through this analysis, Liu et al. [102] discovered that TiF3 is an
Nanometric -Fe/LES6-4B 55.4 ± 4.0 89.7 ± 4.8 excellent LiAlH4 dehydrogenation dopant.
Nanometric -Fe/IMP68-4B 59.5 ± 8.0 76.6 ± 3.2
Zang et al. [95] also stated that TiF3 improves the dehy-
Micrometric -Fe (600 min)/IMP68-4B 87.9 ± 0.2 84.8 ± 0.0
Micrometric -Fe (180 min)/IMP68-4B 95.6 ± 16.8 93.5 ± 0.2
drogenation kinetics and may enhance the hydrogen storage
Micrometric -Fe (60 min)/IMP68-4B 76.2 ± 5.7 85.1 ± 15.0 performance of LiAlH4. They used different mol% of TiF3 (1, 2,
4 and 6 mol% of TiF3). All the samples exhibited two distinct
hydrogen desorption peaks when heated up to 260  C. When
the mol% of TiF3 is increased, the initiation desorption tem-
perature of LiAlH4 is lowered. For the first and second stages of
can decompose into LiAlH4 and Li3AlH6 during milling as fol- desorption, 6 mol% TiF3-doped LiAlH4 can decrease initial
lows: AlCl3 < VBr3 < VCl3. However, the amount of hydrogen desorption temperature of LiAlH4 at 80.5  C and 194  C,
emitted from samples milled with these metal halides is respectively. However, the original desorption temperature
smaller than that from as-milled LiAlH4 (approximately for the undoped LiAlH4 is approximately 179.9  C for the first
2e4 wt% of hydrogen) as a consideration for the hydrogen stage and 216.6  C for the second stage. Despite that, the
capacity. However, LiAlH4 þ AlCl3 indicated a smaller loss of overall amount of hydrogen release for the undoped LiAlH4
hydrogen capacity than that indicated by LiAlH4 þ VBr3 and
LiAlH4 þ VCl3. Smaller hydrogen emission from the milled
samples with halides are due to the dead weight of metal
halides catalyst, which does not contain hydrogen. Similar
outcome was found by Sazelee et al. [104] for the LaFeO3,
where the decrement of hydrogen capacity was reduced less
than 1.0 wt% due to the dead weight of LaFeO3. Furthermore,
study conducted by Yahya and Ismail [90] also indicated that
MgH2 with 20 wt% of the SrTiO3 has a total desorption capacity
of 5.6 wt%, which is 1 wt% lower as compared to the composite
with 10 wt% of the SrTiO3. The reason behind this phenome-
non is due to a dead weight of the SrTiO3, which does not
contain hydrogen.
Liu et al. [102] also suggested that TiF3 would also lower the
temperature of LiAlH4’s onset decomposition. Interestingly,
this analysis also examined the specific impact of ball milling
time between 4 mol% TiF3-doped LiAlH4. Fig. 10 shows the
XRD pattern LiAlH4 þ 4 mol% of TiF3 with different milling Fig. 10 e XRD patterns of (a) as-received LiAlH4 and
times. As Fig. 10 shows, after LiAlH4 þ 4 mol% of TiF3 was LiAlH4 þ 4 mol% of TiF3 after different BMT: (b) 30 min, (c)
milled for 30 min, the diffraction peaks of LiAlH4 became 120 min, (d) 360 min and (e) 1080 min [102].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1
and 6 mol% TiF3-doped LiAlH4 is 7.3 and 5.9 wt%, respectively.
Further investigation regarding the dehydrogenation kinetics
and thermodynamic was a study using differential scanning
calorimetry (DSC). The findings revealed that the activation
energy of the two dehydrogenation reactions for LiAlH4 is
reduced to 66.76 and 88.21 kJ/mol.
Cai et al. [96] examined 1, 2, 4 and 6 mol% of FeCl2-doped
LiAlH4. In their study, the doped samples started releasing
hydrogen at a much lower temperature than the undoped
LiAlH4. The hydrogen started to decompose at 88  C, 76  C,
72  C and 68  C for the LiAlH4 þ x mol% of FeCl2 (where x is 1, 2,
4 and 6), respectively. Additionally, the apparent activation
energy was lowered after the addition of FeCl2, and the par-
ticle size of the samples was decreased. By examining SEM,
the particle size becomes smaller and the changing of LiAlH4
creates more boundaries, thereby improving the dehydriding
performance of LiAlH4 samples. The DSC results better
described the remarkable catalytic effect of FeCl2 on the
desorption performance of LiAlH4, as shown in Fig. 11. There
are four characteristic peaks for the undoped samples, i.e. two
exothermic peaks and two endothermic peaks. The first
endothermic peak at 163.4  C corresponds to the contact of
LiAlH4 with hydroxyl impurities, whereas the second
exothermic peak at 171.2  C corresponds to the LiAlH4
melting. When the temperature increases, the first endo-
thermic peak appears at 184.8  C and the second exothermic
peak at 240.8  C, leading to the LiAlH4 decomposition as in Eq.
(1) and Li3AlH6 decomposition as in Eq. (2). Interestingly, there
were only two characteristic peaks in the DSC curves, as in
Eqs. (1) and (2), after LiAlH4 was doped with FeCl2. Thus, the
successful reduction of the activation energy barrier confirms
the remarkable enhancement in the hydrogen storage prop-
erties of LiAlH4 after the addition of the metal halide catalysts.
The effects of the addition of NbF5 to the hydrogen storage
properties of LiAlH4 was studied by Ismail et al. [97]. With the
addition of NbF5, the onset desorption temperature and acti-
vation energy of LiAlH4 reduced dramatically. Upon the
introduction of the NbF5, the number of thermal events for the
DSC curves also reduced from 4 to 2. This finding is similar to
that of Balema et al. [98], who reported about LiAlH4 þ 3 mol%
Fig. 11 e DSC curves of as-received LiAlH4 and LiAlH4-2 mol
% FeCl2 at a heating rate of 10  C/min [96].
9131
Al3Ti. Additionally, the average dehydrogenation rate of NbF5-
doped samples was 5e6 higher than that of the raw LiAlH4. To
analyse the gas released during the dehydrogenation reaction,
a mass spectrometer was utilized. It is revealed that only
hydrogen gas was released from 120  C to 200  C. No other gas
was detected (e.g. HF). Conversely, Jin et al. [105] stated that
throughout high-energy ball milling, NbF5 was proposed to
melt, and this facilitated the forming of extremely thin, film-
like Nb hydride, preferentially along the grain boundaries of
nanocrystalline MgH2. Thus, it can be suggested that the
introduction of NbF5 as a catalyst improves the efficiency of
metal hydride in solid-state hydrogen storage. In the mean-
time, Li et al. [99] investigated the effects of K2TiF6 on the
dehydrogenation properties of LiAlH4. The addition of K2TiF6
significantly lowered the onset desorption temperature,
enhanced the isothermal desorption kinetics and decreased
the activation energy of LiAlH4. Further analysis revealed that
the in situ formation of KH, LiF, TiH2 and Al3Ti facilitated the
hydrogen storage performance of LiAlH4.
Meanwhile, Sun et al. [100] proposed that another metal
halide catalyst (NiCl2) could boost the dehydriding kinetic
performance of LiAlH4. NiCl2 has been shown to dramatically
decrease the onset of desorption temperature and increase
the dehydriding kinetic efficiency of LiAlH4. Interestingly, the
sample can desorb 4.2 wt% of hydrogen at 100  C when NiCl2
was doped with LiAlH4. This 100  C is close to that needed for
practical applications. The NiCl2 is believed to contribute to
the in situ formation of LiAlH4 and active Ni species, which
plays an essential role in the LiAlH4eNiCl2 system. Addition-
ally, Suttisawat and co-workers [103] investigated the catalytic
effect of HfCl4 and ZrCl4 on hydrogen absorption/desorption of
LiAlH4; 4% HfCl4-doped LiAlH4 and 4% ZrCl4-doped LiAlH4
samples began to release hydrogen at 100  C, and the release
temperature was 40  C below than that of the undoped sam-
ples. No hydrogen absorption has been detected for both
doped samples. Meanwhile, Fu et al. [101] prepared 2 mol%
TiCl3-doped LiAlH4 and 2 mol% ZrCl4-doped LiAlH4 powders
that were pelletized at a different compaction pressure. The
result shows that as the compaction pressure increases, the
density of the doped LiAlH4 increases and the dehydrogena-
tion kinetics also improves.
Metal oxide
Hydrogen desorption properties of LiAlH4 ball mill with TiO2
has been investigated by Ismail et al. [106]. The onset tem-
perature for the hydrogen desorption of as-received LiAlH4
was 150  C. The onset of desorption temperature was
decreased to 60  C, and full desorption was done below 200  C
after the addition of 5 wt% of TiO2. Additionally, XRD spectra
were performed for the LiAlH4-doped TiO2 after dehydroge-
nation. The XRD pattern only comprised LiH and Al, which
indicates that the decomposition for the first and second
stages were completed. Another more significant and attrac-
tive aspect is a large number of active sites and defects on the
surface dominated by anatase TiO2, offering more options for
electron transfer and interaction, as shown in Fig. 12 [107].
Consequently, the kinetics of the reaction were enhanced.
From the Arrhenius plot, the activation energy of LiAlH4 also
decreased, and the isothermal dehydrogenation kinetics of
LiAlH4 was faster after the addition of TiO2. The doped sample
9132 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1
can release approximately 4.0 wt% of H2 within 80 min at a
temperature of 70  C.
Li et al. [108] stated that the efficiency of the hydrogen
storage of LiAlH4 can be improved by adding metal oxides
catalysts such as Fe2O3 and Co2O3. The results proved that, for
the first and second stages, the starting desorption tempera-
ture for the 5 mol% Fe2O3-doped LiAlH4 was lowered by 85  C
and 60  C compared with that for the as-received LiAlH4. In the
meantime, for the 5 mol% Co2O3-doped LiAlH4 was decreased
in the first stage by 76  C and in the second stage by 45  C
compared with that for the as-received LiAlH4. The particle
sizes of the doped samples were smaller than those of the
undoped samples. Figs. 13 and 14 indicate the uniform dis-
tribution of Al, O, Fe and Co. They also present that the metal
oxide catalyst (Fe2O3 and Co2O3) was well mixed with LiAlH4
and finely distributed of various Co oxides, Li2Fe2.4O4 and
Fe0.957O by serving as active for nucleation growth of dehy-
drogenated product contributes to the kinetics improvement
of LiAlH4.
Furthermore, Sazelee et al. [109] reported the catalytic ef-
fect of LaFeO3 synthesized by the solid-state method on the
hydrogen storage properties of LiAlH4 system. They observed
that the use of 10 wt% LaFeO3 in the LiAlH4 had lowered the
original desorption temperature to 103  C and 153  C for the
first and second desorption stages, which were decreased by
40  C and 22  C in contrast to the undoped sample. The
measured activation energy was lowered in the first and sec-
ond stages by 34 and 29 kJ/mol, respectively. They also noted
that the particle sizes of the doped samples were smaller than
those of the undoped samples.
Furthermore, Ali et al. [110] reported the addition of
nanolayer MgFe2O4 on the dehydrogenation properties of
LiAlH4, and their result shows that the dehydrogenation rates
were 20 times faster than those of the undoped samples.
Additionally, the activation energy also reduced to 73 kJ/mol
for the first desorption stage and 97 kJ/mol for the second
desorption stage. Further analysis indicates that newly
developed species of MgO, LiFeO2 and Fe generate surface
activation and provide a high number of nucleation sites on
the surface of LiAlH4. Meanwhile, Li et al. [111] substantiated
that the addition of NiCo2O4 improved the hydrogen storage
Fig. 12 e Schematic illustration of hydrogen dissociation
and recombination on the interface of TiO2 [107].
properties of LiAlH4. For the dehydrogenation kinetic test,
within 150 min at 150  C, the doped samples were able to
release approximately 6.47 wt% of hydrogen. However, the
hydrogen released over the same evaluation time for the
undoped sample were reported to be < 1.0 wt%. Additionally,
for the first stage of desorption, the activation energy of the
2 mol% of NiCo2O4 was lowered by 37.08 kJ/mol. Moreover, the
particle size of as received LiAlH4 is larger than 5 mm. After
undergo milling process, the particle size of as milled LiAlH4 is
about 1 mm. This is proved that the milling process also
affected the particles size of the samples. After the addition of
NiCo2O4, the samples are distributed between 100 and 200 nm.
Through the above analysis, small crystallite size results in
introducing high surface defects and creating more grain
boundaries, thus improving hydrogen storage performance of
LiAlH4.
Wang et al. [112] also showed the inclusion of Gd2O3 and
Nd2O3 enhanced the hydrogen release properties of LiAlH4.
However, doping with these metal oxide catalysts has no
obvious effect on the microstructure of LiAlH4. Further
research regarding metal oxide as a catalyst has been con-
ducted by Li et al. [113]. The study proved that the addition of
CoFe2O4 has strengthened the hydrogen storage properties of
LiAlH4. They disclosed that the CoFe2O4 metal oxide used as a
catalyst will reduce the onset desorption temperature to 65  C
compared with 155  C for the as-received LiAlH4. Further
study revealed that the activation energy for the first and
second stages of the LiAlH4 þ 2 mol% CoFe2O4 was 52.4 and
86.5 kJ/mol, which is 42.4 and 86.1 kJ/mol lower than those as-
received LiAlH4, respectively. SEM images shows that as-
received LiAlH4 consists of large irregular polyhedron parti-
cles, up to 40 mm in size. The morphology of as-milled LiAlH4
became as amounts of regular globular particles with diam-
eter ranging from 3 to 10 mm. After the addition of 2 mol%
CoFe2O4, samples are fine but inhomogeneous with average
size of about 6 mm. Smaller in particles size creates more
surface defects and larger amount of reaction nucleation sites,
which resulted an obviously improvement desorption prop-
erties of LiAlH4.
In the study by Rafi-ud-din et al. [114], the performance of
hydrogen storage of LiAlH4 showed dramatic improvement
with the addition of Cr2O3 and Nb2O5 catalysts. They revealed
that the desorption temperature of Cr2O3-doped LiAlH4 was at
130  C. Conversely, Nb2O5-doped LiAlH4 decomposed at 95  C.
The value for the reduction is approximately 55  C and 20  C
for the addition of Nb2O5 and Cr2O3 catalysts, respectively,
compared with that for undoped LiAlH4. Therefore, Rafi-ud-
din et al. [114] shows that adding Nb2O5 and Cr2O3 as cata-
lysts played a critical role in improving the desorption kinetic
of LiAlH4. Wang et al. [115] conducted studies about the
dehydrogenation properties of LiAlH4 with and without CeO2
catalyst. This research resulted in an excellent finding on the
hydrogen storage performance of LiAlH4. The tests of the TPD
revealed that the CeO2-doped samples decreased the tem-
perature of the initiation of desorption, but the overall amount
of hydrogen emitted was only 7.5 wt%. Additionally, the
number of thermal events in DSC measurement was also
decreasing from three to two. The two stages of desorption
lead to one exothermic peak at 128  C and one endothermic
peak at 220  C as in Eqs. (1) and (2), respectively. Further
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1
Fig. 13 e (a) SEM image of as-milled 5 mol % Fe2O3 -doped LiAlH4 and elemental maps of (b) aluminum, (c) oxygen, and (d)
iron [108].
studies have shown that Ce4þ reduction affected Li ability to
donate its charge to AlH4, thereby weakening the AleH bond
and allowing the hydrogen to desorb at a lower temperature.
In addition, the remaining Ce4þ ions serve as a competitor for
the Li atoms to donate charges. This weakening of the
hydrogen metal bond decreases the activation energy and
improves kinetics.
Sazelee et al. [116] reported that the initial desorption
temperature of 10 wt% BaFe12O19-doped LiAlH4 reduced to
95  C for the first decomposition stage and 156  C for the
second decomposition stage. Isothermal desorption kinetics
revealed that 4.2 wt% of hydrogen can be desorbed for 150 min
by 10 wt% BaFe12O19-doped LiAlH4 at 90  C compared with that
by as-received LiAlH4 (<1.0 wt% within the same period).
Additionally, 10 wt% of BaFe12O19 can minimize the particle
sizes of LiAlH4. The hardness of BaFe12O19 can break the LiAlH4
particles, thus the smaller particle sizes of the sample. The
desorption behaviours of LiAlH4 with metal oxide catalysts
(MoO3, Fe2O3, Cr2O3 and ZnO) was conducted by Ismail et al.
[117]. Among these catalysts, Fe2O3 exhibited stronger cata-
lytic performance than Cr2O3, ZnO and MoO3. The Fe2O3 doped
LiAlH4 started to decompose at 80  C for the first step
(decomposition of LiAlH4) and at approximately 145  C for the
second step (decomposition of Li3AlH6). In comparison,
isothermal desorption kinetics suggested that only Fe2O3-
doped LiAlH4 would emit more hydrogen at 90  C for 150 min
(approximately 4.5 wt%). Meanwhile, another doped catalyst
can only release hydrogen of approximately <0.5 wt%. The
XRD pattern showed that the in situ generated Fe0.9740O and
9133
Li5FeO4 provided a synergetic effect in improving the
hydrogen storage performance of LiAlH4.
Metal hydride
Besides metal halides and a metal oxide, another catalyst that
is of considerable interest is metal hydride. Liu et al. [118]
studied the effect of micro- and nano-TiH2 on the hydrogen
storage performance of LiAlH4. As-received LiAlH4 began
dehydrogenating at 155  C and finished at 240  C with 7.6 wt%
of hydrogen. However, after milling for 1 h, hydrogen began to
release at 135  C, which is a 20  C more decrease than that of
as-received LiAlH4. When micro- and nano-TiH2 was doped
with LiAlH4, the temperature of the initiation desorption
dropped significantly to 90  C and 80  C, respectively, as
shown in Fig. 15. Additionally, isothermal desorption kinetics
of LiAlH4 strengthened when doped with TiH2. Noticeably,
hydrogen release from as-received LiAlH4 is reported after
more than 70 min of induction time. The nano-TiH2 doped
LiAlH4 takes only 11 min at 120  C. The improvement of
dehydrogenation properties of LiAlH4 when doped with nano-
TiH2 is believed due to the close interaction between TiH2 and
LiAlH4 during the milling process. The contact between nano
TiH2 and AleH bonds could be more significant with
increasing temperature, causing the substantial catalytic in-
fluence of nano-TiH2. Tena Garcia and his employees [119]
were researching the impact of TiH2 on the dehydrogenation
behaviour of LiAlH4. In fact, the application of TiH2 has had
limited beneficial effects on the dehydrogenation temperature
decline.
9134 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1

Fig. 14 e (a) SEM image of as-milled 5 mol % Co2O3 -doped LiAlH4 and elemental maps of (b) aluminum, (c) oxygen, and (d)
cobalt [108].

Metal carbide catalytic effects of ZrC powder on the desorption properties of

Recent studies have also shown that metal carbide improves LiAlH4 prepared by designed mixing processes were system-
LiAlH4’s efficiency in hydrogen storage. Rafi-ud-din et al. [120] atically investigated by Li and co-workers [124]. From the DSC
investigated the catalytic effects of nano-sized TiC on LiAlH4 results, the as-received LiAlH4 includes four characteristics
desorption behaviours. Fig. 16 shows the thermal desorption peaks. However, after the addition of 5 wt% of metal carbide
profiles of as-received LiAlH4 and LiAlH4 doped with specific catalyst (ZrC), the peaks reduced to 2. Additionally, the ca-
TiC (1, 2, 3, 4 and 5 mol% TiC). The findings revealed that the pacity of LiAlH4/ZrC composite’s dehydrogenation at 145  C,
temperature of the doped samples initiation of desorption has 130  C and 115  C are 5.62, 5.48 and 4.08 wt% of H2,
been reduced compared with that of the undoped samples.
Out of various doped samples, it was observed that the
optimal content was 2 mol% of TiC-doped LiAlH4, indicating
that the maximum desorption potential resulted in approxi-
mately 6.9 wt% of hydrogen.
Additionally, further studies found that, by adding TiC
nanopowder, the dehydrogenation enthalpy as well as the
activation energy was considerably reduced. Upon applying
TiC, the particle sizes of LiAlH4 became smaller. In fact, TiC is
also known for its high strength and hardness, as defined by
Young’s modulus of ~0.5 TPa. The TiC nanoparticles will then
act as a grinding agent for the comparatively soft LiAlH4 ma-
trix. Other studies also reported that the TiC is a good catalyst
for NaAlH4 and Mg2NiH4, acting as a grinding agent during
milling process [121,122]. Additionally, Varin and Pavriz [123]
investigated the dehydrogenation performance of LiAlH4 with
TiC and ZrC. The addition of TiC and ZrC incremental the
decomposition of LiAlH4 to the Li3AlH6 and Al mixture (as in
Eq. (1)) followed by further decomposition of Li3AlH6 to the Al
and LiH mixture (as in Eq. (2)). The XRD findings also indicated Fig. 15 e Onset desorption temperature of as received and
that the interstitial compounds remained stable in the hy- as milled LiAlH4 and LiAlH4 doped with micro- and nano
dride matrix during the entire ball milling duration. The TiH2 [118].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1
respectively, within 180 min. By comparison, the as-received
LiAlH4 shows low kinetic desorption with only 1.39 wt% of
hydrogen released for 180 min at 145  C. The XRD scans were
performed on 5 wt% ZrC þ LiAlH4 after desorption at 250  C
proved that ZrC had high stability. A previous study also found
ZrC to be incredibly hard and thermodynamically more stable
with a strong ZreC bond, which makes it a stable material
[125].
Additionally, Xia and co-workers [126] have extensively
explored the impact of 2D layered Ti3C2 on LiAlH4 dehydro-
genation behaviours. It has been reported that 5 wt% of Ti3C2
doped with LiAlH4 can be reduced to 58.6  C for the initial
desorption temperature as opposed to as-received LiAlH4
(180.1  C). Ti3C2 is known to give an important catalytic effect
on LiAlH4 decomposition. More encouragingly, the apparent
activation energy for the first and second phases were
measured as 79.81 and 99.68 kJ/mol, respectively. Further-
more, the morphology of 5 wt% of Ti3C2-doped LiAlH4 was
decrease and smaller compared with as-received LiAlH4,
resulting in a greater surface area and more grain boundaries
that may improve the kinetics of desorption and decrease the
thermodynamic stability of LiAlH4.
Carbon-based materials
Over the last few years, storage by sorption processes on the
surface of materials has been researched extensively for the
solid-state hydrogen storage. As promising adsorbents for
hydrogen, MOFs, single-walled CNTs (SWNTs), or multiwall
CNTs (MWCNTs) and activated carbons have been proposed.
In this case, the surface of the porous materials is adsorbed
with hydrogen molecules. Conversely, owing to their unique
structure, carbon-based materials are also considered as cat-
alysts to improve the hydrogen storage properties of metal/
complex hydride [6,127e143].
In this context, Hsu et al. [135] have been investigating the
catalytic effect of MWCNTs on the dehydrogenation perfor-
mance of LiAlH4. The thermogravimetric analysis (TGA) re-
sults revealed that adding MWCNTs greatly lowered the initial
hydrogen desorption temperature of LiAlH4. Additionally,
isothermal TGA analysis showed that the desorption kinetics
were enhanced by increasing the desorption rate of the first
step and shortening the induction time. Meanwhile, the re-
sults of isothermal desorption kinetics of as-received LiAlH4
by holding at 120  C for 3 h showed no release of hydrogen.
Conversely, under the same period, 4.0 wt% of hydrogen can
be released by 10 wt% MWCNTs-doped LiAlH4. Reduced par-
ticle sizes are allowing the surface area to increase. It has
contributed to the development of LiAlH4’s dehydrogenation
kinetics.
The six distinct carbon additives that are SWCNTs,
MWCNTs, carbon black, carbon nanopowder, graphite and
graphene were studied by Ismail and co-workers [136]. How-
ever, other carbon-based additives showed no noticeable
improvement in the TPD curves except for SWCNTs.
Furthermore, isothermal desorption kinetics also revealed
that LiAlH4 þ 5 wt% SWCNTs samples desorbed four to five
times faster than all other samples. Additionally, in the case of
LiAlH4 þ 5 wt% SWCNT, compared with the as-received LiAlH4
samples, Fourier-transform infrared spectroscopy reported
the weakening of AleH bonds in the LiAlH4 lattice. SWCNTs
9135
have curved surfaces that belong to the rigid fullerene family,
indicating that SWCNTs might have a higher affinity to the
electrons. In addition, carbon is an electronegative element.
Alkali or alkali earth metal tend to partially contribute their
electron to electronegative carbon when carbon is incorpo-
rated into complex hydride [141]. It is assumed that SWCNTs
will normally have a much greater affinity to Li than Al’s
electrons and hence weaken the AleH bond. This weakening
requires a lower temperature for decomposition and contrib-
utes to increased desorption kinetics. They also concluded
that the substantial improvement in decomposition temper-
ature and desorption kinetics is a synergistic catalytic effect
between the catalytic roles of the amorphous carbon/metallic
particles.
Tan et al. [142] also reported that the dehydrogenation
behaviour of LiAlH4 had improved dramatically after
MWCNTs were applied. The starting desorption temperature
for as-received LiAlH4 is 171  C. However, the starting
desorption temperature was lowered to 148  C after the
addition of 20 wt% of MWCNTs. Additionally, Huma Kumar
et al. [143] studied the catalytic role of the carbon nanofibers
(CNFs) on the dehydrogenation behaviour of LiAlH4 and found
that the dehydrogenation kinetic improved substantially
compared to pure LiAlH4. This improvement is believed to be
due to the catalytic role played by the CNFs in which, during
the milling process, the CNFs may become integrated into the
hydride matrix subsequent an increase in the phase
boundary.
Challenges and prospects of LiAlH4 as a
hydrogen storage material
The most recent developments on the way to boost the
hydrogen storage performance of LiAlH4 have been critically
discussed. Although several catalysts have been tested to
Fig. 16 e Onset desorption temperature of as received
LiAlH4 and LiAlH4 doped with different mol of TiC (1, 2, 3, 4,
and 5 mol% TiC) [120].
9136 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 1 2 3 e9 1 4 1
improve the performance of hydrogen storage of LiAlH4, none
of them is achieving the Department of Energy (DOE) targets.
The main issues must be overcome to realize the reversible
release and uptake hydrogen (cyclability) in LiAlH4, as a solid-
state hydrogen storage material, under moderate temperature
and pressure. Previous studies (theoretical and experimental
works) have shown that the LiAlH4 could reversibly desorb
and absorb hydrogen [114,120,144e149]. However, all the
theoretical and experimental works showed that the LiAlH4
system could absorb hydrogen if higher hydrogen pressure is
applied (>8.0 MPa). This is because LiAlH4 are restricted by
weak reversibility and thermodynamics stability [145,150]. For
instance, Jang et al. [146] predicted that >10.3 MPa of partial
hydrogen pressure is required to induce the hydrogen ab-
sorption reaction of Li3AlH6 / LiAlH4 (first stage reaction)
above room temperature. Furthermore, Ke et al. [147] studied
the thermodynamic functions and pressureetemperature
phase diagram of LiAlH4 via ab initio calculations and found
that equilibrium pressure of ~303 MPa at 170  C is needed to
the second stage reaction (3LiH þ Al þ 3/2H2 / Li3AlH6) to
reversibly absorb hydrogen. Meanwhile, Rafi-ud-din et al. [120]
showed that the second stage reaction of TiC-doped LiAlH4
could be rehydrogenated at 165  C under 9.5 MPa. Addition-
ally, Wang et al. [148] reported that the confinement of LiAlH4
in nanoporous carbon resulted in favorable and novel prop-
erties for hydrogen storage of LiAlH4. These samples could
rehydrogenated at a hydrogen pressure of 7 MPa and 300  C.
From the examples above, hydrogen under the moderate
temperature and pressure is difficult to be absorbed by LiAlH4
because of its thermodynamics stability. Therefore, it is
necessary to find suitable materials to fulfil all the re-
quirements for large-scale applications such as the following:
a. Low cost and low hydrogen release temperature
b. High storage gravimetric capacity as well as more
hydrogen absorption/desorption rates
c. Reversibility and operation at a moderate condition (pres-
sure and temperature)
Indeed, the solid-state hydrogen storage of LiAlH4 should
also be developed and optimized; thus, further research and
development are required. The only remaining goal is to find
the right solid-state hydrogen storage materials, which is
incredibly challenging. Several works are under progression,
including doping catalysts through ball milling techniques,
but this area remains wide open to discovering a suitable
catalyst. There are several opportunities to conduct research
on this issue, which can rely on the listing below:
a. Fundamental understanding including the structure,
thermodynamics and kinetics
b. Consideration of the Department of Energy (DOE) targets as
the criteria, such as low onset desorption temperature
c. Systematic investigations on the system such as the
benefit of nanoscales samples
d. Investigation on reversible absorption and desorption of
hydrogen (cycling) by the LiAlH4ecatalyst system under
moderate pressure and temperature should be the key
motivation. A substantial breakthrough is needed to find a
suitable catalyst to realize the reversible release and
hydrogen uptake in LiAlH4.
Conclusion
LiAlH4 is a promising candidate for hydrogen storage appli-
cations because of its advantages such as higher capacity of
10.5 wt% hydrogen. However, LiAlH4 suffers from several
drawbacks that hamper its commercialization. Several
studies have shown that the process of ball milling would
alter the particle size of the LiAlH4. The smaller particle size
makes a larger surface area and decreased grain size. It
brings more defects, and the defects favour the nucleation of
the molecules and diffusion of hydrogen atoms in the LiAlH4.
It can shorten the diffusion distance of hydrogen atoms, and
more hydrogen can be easily desorbed. Furthermore, the
addition of catalysts such as metal halides, metal oxide,
metal hydride, metal carbide, transition metal, and carbon-
based materials can also enhance the hydrogen storage
properties of LiAlH4. Most of LiAlH4ecatalyst system studies
claimed that the in situ formation of active species play a
critical role in an enhancement of the hydrogen storage
properties LiAlH4. It is also believed that for the inert catalyst
(catalyst not reacted with LiAlH4), the close interaction be-
tween catalyst and LiAlH4 during the milling process would
alter the AleH bonding and furthermore improve the
hydrogen storage properties of LiAlH4. However, the lack of
LiAlH4 as a solid-state hydrogen storage material is reversible
release and uptake hydrogen under moderate condition. For
the future development, the study on reversible absorption
and desorption of hydrogen (cycling) should be the main
target. Furthermore, a significant breakthrough is desired to
realize the LiAlH4 system as a superior material for solid-
state hydrogen storage.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgment
It is sincere thanks to the Universiti Malaysia Terengganu for
financial support of the work through Golden Goose Research
Grant (GGRG) under grant number VOT 55190 and for
providing the facilities to carry out this project.
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