Journal of Alloys and Compounds 465 (2008) 527–533

Preparation of Mg-based hydrogen storage materials

from metal nanoparticles
Huaiyu Shao, Tong Liu, Yuntao Wang, Hairuo Xu, Xingguo Li ∗
Beijing National Laboratory for Molecular Sciences (BNLMS), (The State Key Laboratory of Rare Earth Materials Chemistry and Applications),
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
Received 18 July 2007; received in revised form 26 October 2007; accepted 1 November 2007
Available online 20 February 2008

Abstract
By hydrogen plasma metal reaction method, we obtained Mg, Ni, Co, Cu and Fe nanoparticles. Mg nanoparticles show larger average particle
size than Ni, Co, Cu and Fe ones. From these metal nanoparticles, Mg-based hydrogen storage alloys (Mg2 Ni, Mg2 Co and Mg2 Cu) and hydrides
(Mg2 NiH4 , Mg2 CoH5 and Mg2 FeH6 ) were prepared by solid–solid and gas–solid reactions. Powder X-ray diffraction (XRD) was used to define the
structure and composition information. The preparation results in different atmosphere were compared and discussed. Hydrogen and nanostructure
play important roles in the preparation of Mg-based hydrogen storage alloys/hydrides in convenient conditions from metal nanoparticles.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Hydrogen absorbing materials; Metals and alloys; Gas–solid reactions; Solid–solid reactions; X-ray diffraction

1. Introduction
To achieve the automobile application goal, many kinds of
hydrogen storage materials have been explored and studied.
However, it still remains a long way to satisfy the applica-
tion targets. Among these materials, Mg-based ones are always
attractive to many researchers because of the great abundance,
the light weight of Mg, and high hydrogen capacity of the
hydrides, e.g. 7.6 wt.% for MgH2 , 3.6 wt.% for Mg2 NiH4 ,
4.5 wt.% for Mg2 CoH5 and 5.4 wt.% for Mg2 FeH6 . There are
mainly two difficulties needed to deal with when we study the
Mg-based alloys and work for their industrial application. The
first one is the difficult preparation of the stoichiometric alloys
by conventional melting method because of the large difference
in the vapor pressure and the melting point between Mg and the
other metals (Ni, Co, Cu, Fe, etc.). The second one is the poor
hydrogen storage kinetics of Mg and Mg-based alloys.
For preparation of Mg-based alloys, many methods have
been developed since Reilly and Wiswall synthesized Mg2 Cu
and Mg2 Ni by conventional melting method [1,2]. Among the
Mg-based materials, Mg–Ni system is most widely studied, and
most of the work on Mg–Ni system in the literature used ball
milling/mechanical alloying [3–11] method as the preparation
method. Ball milling technique seems to be an effective way
to prepare nanocrystalline and non-equilibrium samples with
plenty of defects and strains [12]. One main disadvantage of
ball milling method is that the sample could easily be polluted by
steel balls and air, even in very good protection conditions. Other
techniques that are usually used to prepare Mg-based materi-
als include melting [2,13–16], combustion synthesis [17–19],
bulk mechanical alloying [20–24], melting spinning [25–30],
replacement-diffusion method [31], rotation-cylinder [32,33],
laser sintering [34], etc.
Our group has successfully prepared Mg-based hydrogen
storage alloys (Mg–Ni system [35], Mg–Co system [36] and
Mg–Cu system [37]) by sintering of metal nanoparticles in
hydrogen atmosphere. Here we present the full and detailed
work on the preparation of Mg-based systems (Mg–Ni, Mg–Co,
Mg–Cu and Mg–Fe) in different atmospheres (hydrogen, argon
or vacuum) from Mg, Ni, Co, Cu and Fe nanoparticles produced
by hydrogen plasma metal reaction.
2. Experimental details

∗ Corresponding author. Tel.: +86 10 6276 5930; fax: +86 10 6276 5930. The preparation procedures of Mg-based materials including Mg–Ni,
E-mail address: xgli@pku.edu.cn (X. Li). Mg–Co, Mg–Cu and Mg–Fe systems from initial Mg, Ni, Co, Cu and Fe bulk

0925-8388/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2007.11.003
528 H. Shao et al. / Journal of Alloys and Compounds 465 (2008) 527–533

Table 1
Preparation conditions of Mg-based hydrogen storage samples
Sample name Atmosphere Temperature (K) Time (h)

Mg–Ni-1 0.1 MPa argon 653 2

Mg–Ni-2 0.1 MPa argon 703 2
Mg–Ni-3 3 MPa hydrogen (then 553 1 (0.5)
evacuation)
Mg–Ni-4 Vacuum 623 2
Mg–Ni-5 4 MPa hydrogen 623 2
Mg–Ni-6 Evacuation of Mg–Ni-5 623 0.75
Mg–Co-1 Vacuum 623 48
Mg–Co-2 4 MPa hydrogen 623 48
Mg–Co-3 4 MPa hydrogen 673 24
Mg–Co-4 Evacuation of Mg–Co-3 673 0.5
Mg–Cu-1 Vacuum 673 3
Mg–Cu-2 0.1 MPa argon 673 7
Mg–Cu-3 4 MPa hydrogen (then 673 9 (2)
evacuation)
Mg–Cu-4 3 MPa hydrogen (from 573 0.25
Mg–Cu-3)
Mg–Fe-1 Vacuum 673 60
Mg–Fe-2 4 MPa hydrogen 673 24
Fig. 1. Preparation scheme of Mg-based alloys from metal nanoparticles. Mg–Fe-3 4 MPa hydrogen 673 80
Mg–Fe-4 4 MPa hydrogen 723 24
metals are shown in Fig. 1. From the bulk metals, metal nanoparticles were
prepared by hydrogen plasma metal reaction method using the equipment illus-
The phase and structure analysis of the metals, alloys and hydrides samples
trated at Fig. 2. The equipment mainly consists of a reaction chamber and a
was conducted by powder X-ray diffraction (XRD) using an automatic Rigaku
collecting room. Bulk metals (purity >99.7%) were melting and vaporized by
X-ray diffractometer with monochromatic Cu K␣ radiation at a scanning rate
hydrogen–plasma–metal reaction in the chamber under a mixture of 50% Ar
of 4◦ min−1 . The measurements were carried out using a generator voltage of
and 50% H2 gas at 0.1 MPa. The gaseous metals were taken to the collecting
40 kV and a current of 100 mA. The morphology observation in bright-field
room by the circulating gas and were deposited on the filter wall, where metal
was carried out by transmission electron microscope (TEM) using JEOL JEM-
nanoparticles were obtained. Before the nanoparticles were taken out from the
200CX operating at the accelerating voltage of 160 kV.
collecting room, they were passivated by a mixture of argon and air to prevent
the particles from burning.
Mg and M (M = Ni, Co, Cu and Fe) nanoparticles were weighed in a molar 3. Results and discussion
ratio of 2:1, put in acetone solution and mixed by an ultrasonic homogenizer
for 30 min. After being dried, the 2 Mg + M mixture was pressed at 75 MPa into Fig. 3 shows the XRD curves of the obtained metal nanopar-
small pieces, which were about 10 mm in diameter, 0.3 mm in height and 0.1 g ticle samples prepared by hydrogen plasma metal reaction
in weight. These metal mixture pieces were used to prepare Mg–M hydride or method. From the figure, we can see that all of the obtained
alloy samples in hydrogen, argon or vacuum. The mixture piece was put into the
nanoparticles samples show almost single phase. In Fig. 1(a), Mg
reactor and the system was evacuated. Then the system was heated up to certain
temperatures and provided certain atmosphere conditions shown in Table 1. The
obtained samples were named Mg–M-X according to different Mg–M systems
and prepared in various conditions. For example, Mg–Ni-1 sample was 2Mg + Ni
nanoparticle mixture formed in 0.1 MPa argon at 653 K for 2 h.

Fig. 2. Schematic illustration of hydrogen plasma metal reaction equipment for Fig. 3. XRD curves of the obtained metal nanoparticle samples: (a) Mg, (b) Ni,
the production of metal nanoparticles. (c) Co, (d) Cu and (e) Fe.
 H. Shao et al. / Journal of Alloys and Compounds 465 (2008) 527–533
nanoparticle sample shows hexagonal structure (space group:
P63 /mmc). There is a small peak at about 42.9◦ , which is
attributed to the small amount of MgO impurity (less than
1%). The MgO was formed during the passivation process.
The obtained Ni, Co and Cu nanoparticle samples show face-
centered cubic structure (space group: Fm3m). Fe nanoparticle
sample shows body-centered cubic structure (space group:
Im3m). From Fig. 3, we may see that the peak shape of all the
samples is a little broadened, which indicates the nanometer
scale of the samples. One interesting thing is that the peaks in
Ni, Co, Cu and Fe XRD curves are much broader than those
in Mg XRD curve. It seems Ni, Co, Cu and Fe nanoparticles
have much smaller particle size than Mg ones, which will be
confirmed from the TEM results and discussed later.
Fig. 4 indicates the TEM micrographs of the obtained metal
nanoparticles. Ni, Co, Cu and Fe nanoparticles show similar
particle shape. These nanoparticles have a granular structure
and the particles size ranges from several nanometers to tens of
Fig. 4. Bright-field electron micrographs of the obtained metal nanoparticles: (a) Mg, (b) Ni, (c) Co, (d) Cu and (e) Fe.
529
nanometers. The average particle size is about 30–50 nm. The
Mg nanoparticles are hexagonal in structure and the average
particle size is about 300 nm, which is much bigger than Ni,
Co, Cu and Fe particles. The larger size difference in Mg and
M nanoparticles produced by hydrogen plasma metal reaction
method is due to the faster vaporization rate of Mg than the
ones of Ni, Co, Cu and Fe and the higher generation rate of
Mg by this method, which was discussed by Ohno and Uda
[38].
From the metal nanoparticle mixture, different samples are
prepared according to the conditions presented in Table 1. Fig. 5
shows the XRD curves of the obtained Mg–Ni system samples.
Mg–Ni-1 was produced under 0.1 MPa argon at 653 K for 2 h.
After the reaction, the main phases in the sample are Mg and
Ni. There is a small peak at about 20◦ , which is due to the small
amount of formed Mg2 Ni. The reaction equation is
Mg + Ni → Mg2 Ni (1)
530 H. Shao et al. / Journal of Alloys and Compounds 465 (2008) 527–533
Fig. 5. XRD curves of the Mg–Ni system samples: (a) Mg–Ni-1 (0. 1 MPa argon,
653 K, 2 h), (b) Mg–Ni-2 (0. 1 MPa argon, 703 K, 2 h), (c) Mg–Ni-3 (3 MPa
hydrogen, 553 K, 1 h and then evacuated for 30 min), (d) Mg–Ni-4 (vacuum,
623 K, 2 h), (e) Mg–Ni-5 (4 MPa hydrogen, 623 K, 2 h) and (f) Mg–Ni-6 (after
evacuation of Mg–Ni-5 for 45 min).
When the 2Mg + Ni mixture sample was heated at 703 K in
0.1 MPa argon, and kept for 2 h, Mg–Ni-2 sample with mainly
Mg2 Ni phase was obtained. In Mg–Ni-2 sample, there is still
small amount of unreacted Mg and Ni phases. Mg–Ni-3 sam-
ple was produced under 3 MPa hydrogen at 553 K for 1 h and
subsequently evacuated for 30 min. The main phase in Mg–Ni-
3 sample is Mg2 Ni. There are also Mg and Ni phases though
with small amount. The lowest temperature is 553 K at which
we could successfully obtain mainly Mg2 Ni phase sample from
metal nanoparticles and it is about 300 K lower than the tem-
peratures used for Mg2 Ni synthesis from Mg and Ni powders of
micrometer scale in a similar method [39]. Nanostructure plays
an important role in the synthesis process. Metal nanoparticle
samples have a lower melting point because of the smaller size
and larger specific surface area. Moreover, smaller particle size
of nanoparticle samples means shorter diffusion distance during
solid–solid and gas–solid reactions compared with micrometer
scale or larger scale samples. The reactions are expressed as Eqs.
(2) and (3):
Mg + Ni + H2 → Mg2 NiH4 (2)
Mg2 NiH4 → Mg2 Ni + H2 (3)
When we compare sample Mg–Ni-3 with Mg–Ni-1, we can
find that hydrogen atmosphere is much more effective to pre-
pare Mg2 Ni sample than argon. Mg–Ni-4 sample was produced
under 0.1 MPa argon at 623 K for 2 h. From the XRD curve,
we can see that there is no Mg2 Ni phase formed. The sample
remains mainly Mg and Ni phases. Sample Mg–Ni-5 was made
under 4 MPa hydrogen at 623 K for 2 h. Almost single phase
Mg2 NiH4 sample was obtained. There is no obvious Mg or Ni
peak in the XRD curve. After the evacuation of Mg–Ni-5 sam-
ple for 45 min, we obtained Mg–Ni-6 sample, in which only
Mg2 Ni phase is found. When we compare the preparation result
of sample Mg–Ni-4 with samples Mg–Ni-5/Mg–Ni-6, we can
see that hydrogen atmosphere also is an indispensable factor
for the synthesis in these conditions. From Fig. 5, we may con-
clude that it is much more effective for the Mg2 Ni production
in hydrogen atmosphere than in argon or vacuum. The Mg2 Ni
alloys obtained in both argon and hydrogen are nanostructured
although with different average particle size [35]. Nanostructure
and hydrogen atmosphere play important roles in the preparation
process in convenient conditions.
Fig. 6 shows the preparation results in Mg–Co system. Sam-
ple Mg–Co-1 was formed in vacuum at 623 K for 48 h. There is
no Mg2 Co peak observed from the XRD curve. Sample Mg–Co-
2 was produced in 4 MPa hydrogen at 623 K for 48 h. From
the XRD curve (Fig. 6(b)), we can see that the main phase
is Mg2 CoH5 (tetragonal, space group: P42 /mnm). When we
stopped the hydrogenation reaction in preparation process of
sample Mg–Co-2 after 1 h reaction, we obtained a sample with
Mg2 CoH5 , MgH2 and Co phases. So we may conclude that the
formation of Mg2 CoH5 is expressed as Eqs. (4) and (5):
Mg + H2 → MgH2 (4)
MgH2 + Co + H2 → Mg2 CoH5 (5)
Sample Mg–Co-3 was formed in 4 MPa hydrogen at 673 K
for 24 h. We obtained the similar preparation result with sample
Mg–Co-2. The purity of Mg2 CoH5 phase in samples Mg–Co-2
and Mg–Co-3 is 97%. There is a little Co phase impurity in these
two samples. It is difficult to obtain pure Mg2 CoH5 hydride sam-
ple. Zolliker et al. prepared Mg2 CoH5 sample with a purity of
about 75% in weight through a sintering method in the conditions
of 690–720 K, 4–6 MPa hydrogen for several days [40]. Ivanov
Fig. 6. XRD curves of the Mg–Co system samples: (a) Mg–Co-1 (vacuum,
623 K, 48 h), (b) Mg–Co-2 (4 MPa hydrogen, 623 K, 48 h), (c) Mg–Co-3 (4 MPa
hydrogen, 673 K, 24 h) and (d) Mg–Co-4 (after evacuation of Mg–Co-3 for
30 min).
 H. Shao et al. / Journal of Alloys and Compounds 465 (2008) 527–533
group obtained Mg2 CoH5 sample with MgH2 , Mg and Co impu-
rities using ball milling plus sintering method for several days
[41]. Selvam and Yvon obtained almost pure Mg2 CoH5 sample
by high-pressure sintering in the conditions of 9 MPa hydrogen,
723 K for more than 1 week [42]. Huot et al. obtained Mg2 CoH5
sample with a purity of about 30% by mechanical alloying for
20 h and then sintering in 5 MPa hydrogen at 623 K for 1 day.
Sample Mg–Co-4 was produced after the evacuation of sam-
ple Mg–Co-3 for 30 min. Mg2 Co phase (face-centered cubic,
space group: Fd3m, JCPDF no. 44-1149) sample was obtained.
The purity of Mg2 Co in sample Mg–Co-4 is 87%. The impurity
phases are Mg and Co. When we evacuate sample Mg–Co-3 for
24 h, we could obtain Mg2 Co sample with purity of 96% [36].
The yield difference from 87% to 96% is because the formation
of Mg2 Co takes long time. About Mg2 Co alloy, there is some
disagreement in the literature. In the latest Mg–Co phase dia-
gram, there is only one alloy—MgCo2 . However, many groups
reported the existence of Mg2 Co alloy [23,41,43–45]. From
Fig. 6, we also may get the similar conclusion with Mg–Ni sys-
tem that hydrogen atmosphere and nanostructure play important
roles in the Mg–Co system synthesis process.
Fig. 7 presents the preparation results of Mg–Cu system
in vacuum, argon and hydrogen. Sample Mg–Cu-1 was pro-
duced in vacuum at 673 K for 3 h. The main phases in the
obtained sample are Mg2 Cu (orthorhombic, space group: Fddd)
and MgCu2 (face-centered cubic, space group: Fd3m). There
are small amount of unreacted Mg and Cu phases. The purity
of Mg2 Cu is about 70% in weight. The formation reactions of
Mg2 Cu and MgCu2 phase are expressed as
Mg + Cu → Mg2 Cu (6)
Mg + Cu → MgCu2 (7)
Fig. 7. XRD curves of the Mg–Cu system samples: (a) Mg–Cu-1 (vacuum,
673 K, 3 h), (b) Mg–Cu-2 (0. 1 MPa argon, 673 K, 7 h), (c) Mg–Cu-3 (4 MPa
hydrogen, 673 K, 9 h and then evacuated for 2 h) and (d) Mg–Cu-4 (after hydro-
genation of Mg–Cu-3 in 3 MPa at 573 K for 15 min).
531
From the metal nanoparticle samples to produce Mg2 Cu
alloy, we were in a dilemma that when we adjust the reaction
time or the temperature, either more Mg and Cu will remain
unreacted or more MgCu2 impurity will be yielded. A better
preparation result is obtained in Mg–Cu-2, which was prepared
in 0.1 MPa argon at 673 K for 7 h (Fig. 7(b)). The yield of Mg2 Cu
is about 85%. The best result is obtained in hydrogen atmo-
sphere. Mg–Cu-3 was formed in 4 MPa hydrogen at 673 K for
9 h plus following evacuation for 2 h. The yield of Mg2 Cu phase
is 90%. The formation of Mg2 Cu phase in sample Mg–Cu-3
includes Eqs. (4) and (8):
MgH2 + Cu → Mg2 Cu + H2 (8)
Sun et al. reported some exciting results of preparing Mg2 Cu
alloys from micrometer scale materials by ball milling plus
solid-state reactions [46]. We find in our situation, it is not easy
to obtain pure Mg2 Cu alloy from metal nanoparticles only by
sintering synthesis method. When sample Mg–Cu-3 absorbed
hydrogen in 3 MPa hydrogen at 573 K for only 15 min, we
obtained Mg–Cu-4 sample, which consists of only MgCu2 and
MgH2 phases. There is no existent ternary hydride for Mg–Cu-H
system [1]. The reaction is expressed as
Mg2 Cu + H2 → MgH2 + MgCu2 (9)
The preparation results of Mg–Fe system are presented in
Fig. 8. Mg–Fe-1 sample was produced in vacuum at 673 K for
60 h. Only Mg and Fe phases are found in the sample. This result
is not out of expectation for there is no Mg–Fe binary compound.
Sample Mg–Fe-2 was prepared in 4 MPa hydrogen at 673 K for
24 h. Besides Mg and Fe phases, MgH2 phase is also found in this
sample due to Eq. (4). When the 2Mg + Fe metal nanoparticle
mixture reacted in 4 MPa hydrogen at 673 K for 80 h or in 4 MPa
hydrogen at 723 K for 24 h, we obtained samples Mg–Fe-3 and
Mg–Fe-4, which consist of Mg2 FeH6 main phase (face-centered
Fig. 8. XRD curves of the Mg–Fe system samples: (a) Mg–Fe-1 (vacuum,
673 K, 60 h), (b) Mg–Fe-2 (4 MPa hydrogen, 673 K, 24 h), (c) Mg–Fe-3 (4 MPa
hydrogen, 673 K, 80 h) and (d) Mg–Fe-4 (4 MPa hydrogen, 723 K, 24 h).
532 H. Shao et al. / Journal of Alloys and Compounds 465 (2008) 527–533
cubic, space group: Fm3m) with the purity higher than 90% as
well as a little unreacted Fe. The reactions could be expressed
as Eq. (4) and (10):
MgH2 + Fe + H2 → Mg2 FeH6 (10)
From our results, among these Mg-based system hydrides,
Mg2 FeH6 is the most difficult one to prepare. Didisheim et al.
[47] produced Mg2 FeH6 in 2–12 MPa hydrogen at about 773 K
for 2–10 days. Selvam and Yvon [42] obtained Mg2 FeH6 in sim-
ilar conditions (9 MPa hydrogen, up to 773 K for 10 days). Huot
et al. [48] tried a much more convenient way (ball milling plus
sintering) and they obtained Mg2 FeH6 sample with about 65%
purity. They also tried directly synthesizing Mg2 FeH6 by ball
milling in hydrogen [49] and they reached a yield of about 56%.
After that, mechanical alloyings in different conditions [50–56]
are widely used to prepare Mg2 FeH6 sample. Mg2 FeH6 shows
the larger hydrogen capacity than Mg2 NiH4 and Mg2 CoH5
hydrides, but there is not much work done in the literature
on Mg–Fe-H system due to the difficulty in synthesizing pure
samples and poor hydrogen storage properties.
4. Conclusions
(1) Mg, Ni, Co, Cu and Fe nanoparticles are obtained by hydro-
gen plasma metal reaction method. Mg nanoparticles have
an average size of about 300 nm. Ni, Co, Cu and Fe nanopar-
ticles show mean particle size of about 30–50 nm.
(2) From 2Mg + M metal nanoparticle mixture samples,
Mg-based alloys: Mg2 Ni, Mg2 Co and Mg2 Cu and Mg-
based hydrides: Mg2 NiH4 , Mg2 CoH5 and Mg2 FeH6
are successfully prepared under different atmosphere
(argon/vacuum/hydrogen). Main phase Mg2 Ni sample can
be obtained at 553 K in 3 MPa hydrogen. Mg2 Ni is the
easiest one to produce among these alloys/hydrides and
Mg2 FeH6 is the most difficult one to prepare.
(3) Hydrogen atmosphere is more effective to prepare Mg-
based alloys than argon or vacuum. Hydrogen and
nanostructure play important roles in the synthesis of Mg-
based materials in convenient conditions.
Acknowledgements
The authors acknowledge the National Natural Science Foun-
dation of China (Nos. 20221101, 10335040 and 20671004),
MOST of China (No. 2006AA05Z130) and MOE of China (No.
707002).
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