international journal of hydrogen energy 35 (2010) 2786–2790

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Microstructure and hydrogen storage characteristics of

nanocrystalline Mg D x wt% LaMg2Ni (x [ 0–30) composites

Xuezhang Xiao, Guangcheng Liu, Shuke Peng, Kairong Yu, Shouquan Li,
Changpin Chen, Lixin Chen*
Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, Zhejiang Province, China

article info abstract

Article history: The nanocrystalline Mg þ x wt% LaMg2Ni (x ¼ 0, 5, 10, 20, 30) composites were prepared by
Received 8 April 2009 reactive ball-milling, their microstructure and hydrogen storage characteristics were
Accepted 5 May 2009 investigated. The results show that the addition of LaMg2Ni improves the hydriding rate
Available online 29 May 2009 and capacity. The hydriding capacity of the Mg þ x wt% LaMg2Ni (x ¼ 5, 10, 20, 30)
composites are all above 4.1 wt% at 120  C and above 4.3 wt% at 180  C within 6000 s.
Keywords: Moreover, the addition of LaMg2Ni also improves the dehydriding performance of the
Mg-based composites composites. The main reason for the improvement of hydriding/dehydriding properties
Nanocrystalline investigated by XRD and SEM shows that the synergistic effect among the multiphase
Hydrogen storage property nanocrystalline Mg-based structures make hydrogen easily absorbed/desorbed on the
Reactive ball-milling interface of the matrix.
ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction improved hydrogen storage properties of Mg-based materials,

the nanocrystalline Mg þ x wt% LaMg2Ni (x ¼ 0, 5, 10, 20, 30)
Magnesium-based materials have been intensively investi- composites were prepared by reactive ball-milling under
gated as promising candidates for hydrogen storage due to hydrogen atmosphere, and their hydrogen storage charac-
their high hydrogen storage capacity (7.6 wt%), low cost and teristics and microstructure were investigated.
light weight [1]. However, the application of Mg-based mate-
rials is hindered by their slow kinetics and relatively high
operating temperature. In order to overcome these draw-
2. Experimental
backs, the addition of certain lanthanide series metals [2,3]
and alloying some intermetallic compounds [4,5] with Mg-
The purity of Mg, La and Ni used as raw materials was above
based alloys have been considered by many researchers.
99%. The as-cast LaMg2Ni compound was prepared by induc-
Moreover, it was reported that the intermetallic compound
tion mel ting under the protection of super-pure argon
LaMg2Ni easily reacted with hydrogen at about 170  C, and its
atmosphere, and then mechanically pulverized into particles
absorption/desorption kinetic property and reversibility were
below 200 meshes (76 mm). The Mg powder (99%, 100–200
good [6]. It had been found that nanocrystalline Mg-based
mesh) was mixed with the above LaMg2Ni powder in desig-
hydrogen storage materials prepared by ball-milling exhibited
nated weight ratio. Each mixture was introduced into a stain-
remarkable improvement of hydriding/dehydriding kinetics
less steel vial together with stainless steel balls, and milled in
[7]. In this work, based on the above multiple effect on the
a planetary-type ball mill (QM-4F) under supra-pure hydrogen

* Corresponding author. Tel./fax: þ86 571 8795 1152.

E-mail address: lxchen@zju.edu.cn (L.X. Chen).
0360-3199/$ – see front matter ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.05.024
 international journal of hydrogen energy 35 (2010) 2786–2790 2787

of 0.5 MPa. The ball-milling process was carried out for 20 h at

a rotating speed of 200 rpm together with ball-to-powder
weight ratio of 30:1.
The hydrogen absorption/desorption properties of the
obtained Mg þ x wt% LaMg2Ni (x ¼ 0, 5, 10, 20, 30) composites
were measured on a Sievert’s equipment. Each sample was
first taken out about 1.0 g to put into the stainless steel reactor,
and then the reactor was evacuated to vacuum of 102 bar.
After full activation twice at 340  C, the hydriding temperature
range was 60 w 180  C with 3.5 MPa hydrogen pressure, and
the dehydriding temperature was 180 w 300  C against
0.1 MPa pressure. The phase structures and morphologies of
the samples were determined by X-ray diffraction (XRD,
Rigaku D/max-3B) and scanning electron microscopy (SEM,
Philips-XL30) respectively.

Fig. 2 – XRD patterns of Mg D x wt% LaMg2Ni (x [ 0–30)

3. Results and discussion composites (the top right corner shows the magnifications
as 2q is 31 w 388).
3.1. Microstructure

Fig. 1 shows the XRD pattern of the as-cast LaMg2Ni micro-stress may also play a major role in the change of
compound. It is found that LaMg2Ni main phase exists diffraction peaks. In fact, the measurements of the width at
together with a few LaMgNi4 as minor phases in the half-maximum of the peaks confirm that the grain size of Mg
compound. The XRD patterns of Mg þ x wt% LaMg2Ni decreases to below 70 nm after ball-milling with LaMg2Ni as
(x ¼ 0–30) composites are presented in Fig. 2. The results show shown in Fig. 3. As the LaMg2Ni content x increases from 5 to
that some new phases appear in the XRD patterns of the 30, the grain size of Mg decreases from 61.1 nm to 50.4 nm,
Mg þ x wt% LaMg2Ni (x ¼ 5–30) composites after ball-milled and the microstrain in the crystal lattice increases first and
under hydrogen for 20 h. It can be seen that the main phase is then decreases.
still MgH2/Mg, and a few other phases are LaNi5Hx (x ¼ 0–6), Fig. 4 shows the SEM micrographs of the Mg þ x wt%
Mg6Ni and LaMg2 in Fig. 2. It indicates that some part of LaMg2Ni (x ¼ 5–30) composites. It is found that many small
hydrogen from milling atmosphere dissolves in Mg and finally
forms MgH2. With the increase of LaMg2Ni content in the
composites, more LaNi5 phase is formed, and more LaNi5Hx
appears accordingly. Moreover, it can be seen from the
magnifications of Fig. 2 as 2q ¼ 31 w 38 that, the width at half-
maximum of the peaks of Mg broadens with the increase of
LaMg2Ni content, which suggests that the LaMg2Ni introduced
can help to decrease the grain size of Mg and form the abun-
dant defects in the composites. Lattice deformation and

Fig. 3 – Microstrain and crystallite size of Mg for the

Fig. 1 – XRD pattern of the as-cast LaMg2Ni compound. Mg D x wt% LaMg2Ni (x [ 0–30) composites.
2788 international journal of hydrogen energy 35 (2010) 2786–2790
Fig. 4 – SEM micrographs of the Mg D x wt% LaMg2Ni composites: (a) x [ 5; (b) x [ 10; (c) x [ 20; (d) x [ 30.
particles distribute on the surface of composite matrix, the
corresponding EDX results indicate that the composition of
matrix mainly contain Mg, and the compositions of small
particles are La, Mg, and Ni. The proportion of the small
particles increases with increasing LaMg2Ni content. It can be
found that the size of some small particles for the ball-milled
composites is below 100 nm, which is confirmed by the above
XRD analysis result. Moreover, the nanocrystalline La–Ni, Mg–
Ni and La–Mg particles resulting in more grain-boundary
regions for the composites can afford facilities for hydrogen
dissociation/recombination [8].
3.2. Hydrogen storage properties
Fig. 5 shows the hydriding curves of Mg þ x wt% LaMg2Ni
(x ¼ 0–30) composites at various temperatures. The hydrogen
absorption capacities of the composites are also presented in
Table 1. It is found that the hydriding rates and capacities of
Mg þ x wt% LaMg2Ni (x ¼ 5–30) composites are better than the
pure Mg powders milled without LaMg2Ni at various temper-
atures. For example, the hydriding capacities of Mg þ x wt%
LaMg2Ni (x ¼ 5–30) composites are all above 4.1 wt% at 120  C
and above 4.3 wt% at 180  C within 6000 s, but the hydriding
capacity of pure Mg is only 2.31 wt% at 180  C within 6000 s.
This indicates that the ball-milling with LaMg2Ni for Mg can
improve its absorption properties markedly, even at lower
temperature (60  C). The improved hydrogen storage property
may be related to the variation of grain size and multiphase
nanocrystalline for the ball-milled composites, which will be
discussed below. However, the Mg þ 5 wt% LaMg2Ni
composite shows the best hydriding performance at 180  C. At
lower temperature (60–120  C), the hydriding performances of
Mg þ x wt% LaMg2Ni (x ¼ 10, 20, 30) composites are better than
that of Mg þ 5 wt% LaMg2Ni composite. Moreover, the
hydriding performances are improved with the increase of
temperature, indicating that the temperature affects greatly
on the absorption properties of the composites.
The hydrogen desorption properties of the composites
were measured after the Mg þ x wt% LaMg2Ni (x ¼ 0–30)
composites fully hydrogenated at 300  C for 10 h. Fig. 6 shows
the dehydriding curves of Mg þ x wt% LaMg2Ni (x ¼ 0–30)
composites at 300  C. It can be seen that, the dehydriding
property of the pure Mg powder ball-milled without LaMg2Ni
is very poor, however, introducing LaMg2Ni into Mg can
greatly improve its desorption property. With the increase of
LaMg2Ni content, the dehydriding rate and capacity of the
composites first decrease and then increase. The Mg þ 5 wt%
LaMg2Ni composite exhibits the best desorption capacity,
reaching 4.4 wt% in 1800 s. Then, the dehydriding properties
of Mg þ 5 wt% LaMg2Ni at lower temperatures (180  C, 220  C
and 260  C) were further investigated, as shown in Fig. 7. It can
be found that the dehydriding rate and capacity of Mg þ 5 wt%
LaMg2Ni increase from 0.67 wt% to 1.14 wt% with increasing
the temperature from 180  C to 260  C, which are all lower
than that (4.4 wt%) of the same composite at 300  C, but higher
than the pure Mg milled without LaMg2Ni at 300  C. These
results indicate that ball-milling with LaMg2Ni can improve
not only the hydriding property but also the dehydriding
property of Mg-based composites.
The addition of LaMg2Ni into Mg is advantageous for
the enhancement of hydriding/dehydriding properties of
the composites as shown above. Combining with the
 international journal of hydrogen energy 35 (2010) 2786–2790 2789

Fig. 5 – Hydriding curves of Mg D x wt% LaMg2Ni (x [ 0–30) composites at various temperatures.

microstructure analysis, the improvement of the hydriding/ and afford facilities for hydrogen dissociation/recombination
dehydriding properties can be explained as follows. First, ball- in the grain-boundary region [8]. Thus the hydriding/dehy-
milling under hydrogen atmosphere causes the significant driding reaction of Mg-based composites could be more
refinement of the microstructure, giving rise to the decrease of effective and easier, and the hydriding/dehydriding thermo-
grain size and inducing abundant defects in the composite as dynamics could be improved [10]. Third, the ball-milled
evidenced in Fig. 2, which can create more fresh surfaces and Mg þ x wt% LaMg2Ni composites form the multiphase
active locations to accelerate the diffusion of hydrogen, and
improve its hydrogen absorption/desorption kinetics [9].
Second, reducing the grain size to nanometer range and
forming more grain-boundary regions of the composites can
also form the unstable nanocrystalline hydride in the matrix

Table 1 – The hydrogen absorption capacities of

Mg D x wt% LaMg2Ni (x [ 0–30) composites at various
temperatures.
Samples Hydrogen absorption capacity (wt%)

At 60  C in At 120  C in At 180  C in
6000 s 6000 s 6000 s

x¼0 0.81 0.84 2.31

x¼5 1.50 4.29 5.41
x ¼ 10 2.43 4.76 5.04
x ¼ 20 2.54 4.68 5.09
x ¼ 30 2.67 4.11 4.34 Fig. 6 – Dehydriding curves of Mg D x wt% LaMg2Ni
(x [ 0–30) composites at 300 8C.
2790 international journal of hydrogen energy 35 (2010) 2786–2790
Fig. 7 – Dehydriding curves of Mg D 5 wt% LaMg2Ni
composite at various temperatures.
nanocrystalline, such as La–Ni, Mg–Ni and La–Mg phases on
the surface of matrix, which could act as nucleation sites for
hydride [8]. In a word, the synergistic effect among the
multiphase nanocrystalline of this Mg-based composites
results in the advantage of hydrogen moving into or leaving
from the disordered interface phase [11], which is ascribed to
the improvement of hydriding/dehydriding properties at
various temperatures.
4. Conclusions
Nanocrystalline Mg þ x wt% LaMg2Ni (x ¼ 5, 10, 20, 30)
composites prepared by reactive ball-milling have better
hydrogen absorption properties at various temperatures than
the pure Mg ball-milled without LaMg2Ni. The hydriding
capacities of these composites reach beyond 4.1 wt% at 120  C
and beyond 4.3 wt% at 180  C within 6000 s, however, that of
the pure Mg is only 2.31 wt% at 180  C. Moreover, the
Mg þ 5 wt% LaMg2Ni composite shows the best hydriding
performance at 180  C and the best dehydriding performance
at 300  C. As the LaMg2Ni content (x) increases from 5 to 30, the
grain size of Mg decreases from 61.1 nm to 50.4 nm. The
addition of LaMg2Ni improves the hydrogen hydriding/dehy-
driding properties of Mg-based composites obviously. It is
found further that the decrease of grain size, formation of
abundant defects and grain-boundary regions in the
composite, and multiphase nanocrystalline structures,
together result in the improvement of hydriding/dehydriding
performances at various temperatures.
Acknowledgments
This work is jointly supported by the National High Tech-
nology Research and Development Program of China
(2006AA05Z144), the National Key Program for Basic Research
of China (2007CB209700) and Zhejiang Provincial Science &
Technology Program of China (2006C11233).
references
[1] Brumfiel G. Hydrogen cars fuel debate on basic research.
Nature 2003;422:104.
[2] Wang XL, Tu JP, Wang CH, Zhang XB, Chen CP, Zhao XB.
Hydrogen storage properties of nanocrystalline Mg-Ce/Ni
composite. J Power Sources 2006;159:163–6.
[3] Huot J, Pelletier JF, Lurio LB, Sutton M, Schulz R. Investigation
of dehydrogenation mechanism of MgH2-Nb
nanocomposites. J Alloys Compd 2003;348:319–24.
[4] Vijay R, Sundaresan R, Maiya MP, Srinivasa S, Fu Y, Klein HP,
et al. Characterisation of Mg-x wt.% FeTi (x=5-30) and Mg-40
wt.% FeTiMn hydrogen absorbing materials prepared by
mechanical alloying. J Alloys Compds 2004;384:283–95.
[5] Bobet JL, Grigorova E, Khrussanova M, Khristov M, Radev D,
Peshev P. Hydrogen sorption properties of the
nanocomposites Mg-Mg2Ni1-xFex. J Alloys Compd 2002;345:
280–5.
[6] Chio MD, Schiffini L, Enzo S, Cocco G, Baricco M. Hydrogen
absorption and desorption in nanocrystalline LaMg2Ni. J
Alloys Compds 2007;434–435:734–7.
[7] Zaluska A, Zaluski L, Strom-Olsen JO. Nanocrystalline
magnesium for hydrogen storage. J Alloys Compd 1999;288:
217–25.
[8] Orimo S, Fujii H. Materials science of Mg-Ni-based new
hydrides. Appl Phys A 2001;72:167–86.
[9] Rudman PS. Hydriding and dehydriding kinetics. J Less-
Common Met 1983;89:93–110.
[10] Delchev P, Himitliiska T, Spassov T. Microstructure and
hydriding properties of ball-milled Mg-10 at.%MmNi5 (Mm =
La, Ce-rich mischmetal) composites. J Alloys Compd 2006;
417:85–91.
[11] Zhu M, Gao Y, Che XZ, Yang YQ, Chung CY. Hydriding
kinetics of nano-phase composite hydrogen storage alloys
prepared by mechanical alloying of Mg and MmNi5–
x(CoAlMn)x. J Alloys Compd 2002;330–332:708–13.