Journal of Materials Synthesis and Processing, Vol. 8, No.

1, 2000

Production of Hydrogen Storage Alloy of Mg2NiH4 by

Hydriding Combustion Synthesis in Laboratory Scale

Liquan Li,1 Tomohiro Akiyama,2 and Jun-ichiro Yagi3

A laboratory scale production method for hydrogen storage alloy of Mg2 NiH4 by hydriding
combustion synthesis was investigated. In this study, cylinders of magnesium and nickel mixture
powder, compressed at different pressures, and a powder mixture of metals, without the compressive
treatment, were used as a raw material. The products were examined by X-ray diffraction (XRD)
and scanning-electron microscopy (SEM). The XRD results indicated that pure Mg2 NiH4 was
simply obtained not only from the compressed cylinders, but also from the powder. There was
no significant effect of the compressive pressure of the cylinder on the composition of the final
products. However, SEM observations showed that the compressed sample and the powder are
clearly different, in spite of the same product composition. The results also revealed a possibility
of new production system of Mg2 NiH4 using hydriding combustion synthesis, with many benefits
of simple pretreatment, including: simple equipment, short operating time, high-quality product,
and energy savings.

KEY WORDS: Hydrogen storage; intermetallics; miscellaneous; reaction synthesis.

INTRODUCTION a specific chemical composition. In addition, for prac-

Magnesium-based alloys are potentially important
hydrogen storage materials because of their light weight,
high specific storage capacity, abundant raw materials,
low environmental impact, and numerous applications.
For example, based on its high-temperature characteris-
tics of hydriding and dehydriding, it has been proposed
as a heat-storage/ transportation medium in steelworks
[1]. However, the conventional ingot process essentially
cannot produce this alloy because magnesium evapo-
rates easily due to its high vapor pressure [2]. Thus, a
repeated remelting process with an additional supply of
magnesium is needed to prepare the Mg2 Ni alloy with
1Department of the Materials Science and Engineering, Nanjing Uni-
versity of Chemical Technology, 5, Xinmofan Road, Nanjing, 210009,
P.R. China.
2 Department of Chemical Engineering, Osaka Prefecture University.
1-1 Gakuen-cho, Sakai, Osaka, 599-8531, Japan.
3 Institute for Advanced Materials Processing, Tohoku University 1-1,
Katahira, 2chome Aobaku, Sendai, 980-8577, Japan.
tical use, the product must be activated by at least ten
hydriding/ dehydriding cycles, after a crushing process,
to form Mg2 NiH4 [3].
The production of a magnesium nickel alloy of
Mg2 Ni by combustion synthesis was proposed in 1995
[4, 5]. Combustion synthesis or self-propagation high-
temperature synthesis (SHS) [6], which is based on
a high exothermic reaction, is a newly developed
materials-processing technology offering many advan-
tages, such as short processing time, simple equipment,
high product purity, low energy requirements, etc. [7]. In
this method, a compact of well-mixed magnesium and
nickel powders with 2 : 1 molar ratio is heated in an
inert gas atmosphere. The compact quickly gives pure
Mg2 Ni by means of an exothermic solid–solid reaction.
Moreover, the process of direct synthesis of magnesium
nickel hydride Mg2 NiH4 from the mixture of magne-
sium and nickel was proposed in 1997 [8]. The process
named hydriding combustion synthesis, encompasses the
combustion synthesis of Mg2 Ni, conducted in an atmo-

7
1064-7562/ 00/ 0100-0007$18.00/ 0  2000 Plenum Publishing Corporation
8 Li, Akiyama, and Yagi
sphere of hydrogen, for the simultaneous hydriding reac-
tion of Mg2 NiH4 . Following this, a systematic investi-
gation of this process is initiated. However, all of these
studies were limited to small samples (several ten of mil-
ligrams), from the cracking of the compact of the pow-
der mixture of magnesium and nickel, because of limi-
tations of the apparatus, such as DSC and TG-TDA. For
industrializing the process of hydriding combustion syn-
thesis of Mg2 NiH4 , we need to further investigate the
process in larger scale production. In this paper, there-
fore, we describe a new apparatus designed specifically
for this objective. We then report the results of hydriding
combustion synthesis of Mg2 NiH4 from the compressed
cylinder of magnesium and nickel mixture, as well as
directly from the powder mixture of these metals.
BACKGROUND OF THE HYDRIDING
COMBUSTION SYNTHESIS
The effect of hydrogen pressure on the hydriding
combustion synthesis of Mg2 NiH4 in 0.5, 1.0, 2.0, and
4.0 MPa hydrogen was studied by differential scanning
calorimeter (DSC) [9]. It was observed that there are four
sharp peaks on the heat flow curves during the heating
and cooling periods between room temperature and 850
K. Two peaks (first and second peaks) are endothermic
and occur during the heating period. Two other peaks
(third and fourth peaks) are exothermic and occur during
the cooling period. The second and fourth peaks always
appear at fixed temperatures, but the first and third peaks
are changeable, depending on hydrogen pressure. With
increasing hydrogen pressure, peaks 1 and 3 move into
higher temperature ranges. These results indicate that
the hydriding combustion synthesis of Mg2 NiH4 is not a
simple reaction that it can be expressed by a single reac-
tion formula, such as 2Mg + Ni + 2H2 c Mg2 NiH4 , but a
complicated process, in which there are several endother-
mic and exothermic reactions with pressure dependence.
A study of the reaction mechanism of hydriding
combustion synthesis of Mg2 NiH4 was conducted by
means of DSC and X-ray diffraction (XRD) [10]. It
was reported that hydriding combustion synthesis of
Mg2 NiH4 from the compact of elemental magnesium
and nickel mixture in 2.0 MPa hydrogen, consisted of
seven reactions, detected from the peaks of heat flow in
the DSC curve and from the XRD analysis: (1) Mg + H2
r MgH2 , with a wide temperature range from about 520
to 660 K; (2) MgH2 r Mg + H2 , between about 675 to
700 K; (3) 2Mg + Ni r Mg2 Ni (L), an eutectic reac-
tion of the Mg–Ni system; (4) 2Mg + Ni r Mg2 Ni, from
about 675 to 840 K; (5) Mg2 Ni + 0.15H2 r Mg2 NiH0.3 ,
a solid-solution reaction during the cooling period; (6)
Mg2 Ni + 2H2 r Mg2 NiH4 (HT), between about 645 to
600 K; and (7) Mg2 NiH4 (HT) r Mg2 NiH4 (LT), initiat-
ing at 510 K. Before the formation of Mg2 NiH4 , Mg2 Ni
was formed. The Mg2 NiH4 was produced by hydriding
Mg2 Ni at a high temperature to form, first, a high-tem-
perature type of Mg2 NiH4 (HT), followed by a phase
transformation from the high- to the low-temperature
type of Mg2 NiH4 (LT).
An in situ XRD study of hydriding combustion syn-
thesis of Mg2 NiH4 , within two cycles of temperature
scanning in 16.7 × 10 − 3 K/ s rate under 1.0 MPa hydro-
gen, was reported [11]. The result is that after the sec-
ond cycle of cooling, the Mg2 Ni was not fully trans-
formed to the hydride product of Mg2 NiH4 and the con-
tent of Mg2 NiH4 in the sample after the second cycle of
hydriding is much more than that seen in the sample after
the first cycle of hydriding. Although only one phase of
Mg2 Ni existed in the sample after both the heating peri-
ods of cycles 1 and 2, the XRD intensity of Mg2 NiH4
after the second cycle of cooling was six times that after
the first cycle of cooling. This result indicated that the
hydriding activities of Mg2 Ni, produced after the first
and the second periods of heating, were very different
and that to obtain the full hydride of Mg2 NiH4 , further
cycles of temperature scanning (activation process) are
needed [12].
It is clear that the advantage of the hydriding com-
bustion synthesis of Mg2 NiH4 is not the activation treat-
ment. In order to produce Mg2 NiH4 by hydriding com-
bustion synthesis within the primary cycle of temper-
ature scanning, without any activation, by controlling
the process parameters, the effects of the cooling rate
in temperature scanning and pressure of the hydrogen
atmosphere had to be investigated using thermogravime-
try (TG) and XRD [13]. The results demonstrated that
we can produce pure Mg2 NiH4 by accurately controlling
pressure and thermal conditions within only one cycle of
temperature scanning, according to overall reaction:
2Mg + Ni + 2H2 r Mg2 NiH4
The selected conditions of the two parameters for obtain-
ing pure product were 4.0 MPa hydrogen pressure and
16.7 × 10 − 3 K/ s cooling rate.
Production of Hydrogen Storage Alloy of Mg2NiH4
EXPERIMENT
Apparatus
Figure 1 gives the schematic diagram of the high-
pressure synthesis furnace used in this study. Some char-
acteristics of the furnace are a maximum pressure of 6.0
MPa, a maximum temperature of 1073K, and a uniform
temperature region of 200 mm. As shown in Fig. 1, there
are three zones in the furnace (zone 1–3). Each zone con-
tains a set of electric resistance wires, wired indepen-
dently, to maintain the long uniform temperature region.
The temperature of each zone is controlled through two
thermocouples, one of which is inside and the other is
outside the furnace tube. A ceramic boat, 20 mm wide,
15 mm deep and 150 mm long, is used to contain the
samples, which is set in the middle of the furnace using
a 50-mm i.d. tube composed Icoloy. Before the experi-
ment, the furnace is evacuated to 10 − 5 Pa using a rotation
evacuative system.
Fig. 1. Schematic diagram of the furnace used in hydriding combustion synthesis of Mg2 NiH4 .
9
Sample Preparation
The samples were prepared from commercially
available magnesium and nickel powders, as in the pre-
vious study [8]. The powders of Mg and Ni, with 99.9
mass % in purity and − 177 mm particle size for Mg and
2–3 mm for Ni were mixed well in 2 : 1 molar ratio by
an ultrasonic homogenizer in acetone. After completely
drying in air, some of the well-mixed powder was com-
pressed, by a uniaxial single-acting press at different
pressures, to form cylinders, weighing 2.0 g, 10 mm in
diameter. Some of the powder mixture was used directly
as a sample; these samples also weighed 2.0 g. Table I
gives the conditions of the five samples in this study.
The differences among samples 1, 2, 3, 4, and 5 are the
compressive pressures, which are 1100, 550, 280, and
140 MPa for samples 1, 2, 3, and 4, respectively. For
sample 5, only the powder mixture was used with no
compression.
The thermal conditions of all samples were the
10
Fig. 2. Thermal profile of hydriding combustion synthesis of
Mg2 NiH4 .
same, as shown in Fig. 2. It was first heated to 873 K and
the temperature maintained for 30 min. Then the sam-
ples were cooled to 680 K and maintained for another
30 min. After that, the furnace was powered off and the
samples allowed to cool to room temperature. Hydro-
gen (4.0 MPa) was used as the synthesis atmosphere.
The temperature selected promoted the hydriding reac-
tion of Mg2 NiH4 , which was determined from our pre-
vious study [9]. By this production system, the heating
time from 300 to 873 K is about 50 min, the cooling time
from 873 to 680 K is another 50 min, and the time from
680 to 500 K, which is near the phase-transformation
temperature (510 K) from Mg2 NiH4 (HT) to Mg2 NiH4
(LT) [14], is about 90 min.
RESULTS AND DISCUSSION
Figure 3 is a photograph of samples 1, 2, 3, 4, and
5 after the hydriding combustion synthesis. Samples 1,
2, 3, and 4 were placed on the same boat and were
thermally treated at the same time. All of these sam-
ples are brown in color, which is the typical color of
Mg2 NiH4 , except for samples 4 and 5, which had a thin
surface, slightly grey in color. From XRD analysis, the
grey layer contains some MgO, which comes from an
impurity in hydrogen gas. It is not clear why there is a
relation between the contact condition of particles in raw
materials and the ease of oxidation of magnesium.
Figure 4 is XRD patterns of samples 1, 2, 3, 4, and
5 after synthesis. The patterns indicate that all samples
are the same as Mg2 NiH4 without any significant differ-
Li, Akiyama, and Yagi
Fig. 3. Photograph of samples of hydriding combustion synthesis of
Mg2 NiH4 .
ence, although the compressive pressure of these cylin-
ders are very different, as shown in Table I. Only the
powder mixture of magnesium and nickel was used in
sample 5. The XRD results shown in Fig. 4, therefore,
indicate that before the hydriding reaction of Mg2 NiH4 ,
each of the cylinders had to be in a similar condition for
the hydriding reaction.
To understand this result, we should consider the
aforementioned information together with the reac-
tion mechanism of hydriding combustion synthesis of
Mg2 NiH4 , which was reported in Ref. [10]. In fact,
there are seven reactions occurring during the hydrid-
ing combustion synthesis of Mg2 NiH4 . During the heat-
ing period, Eqs. (1) a hydriding reaction, (2) a dehydrid-
ing reaction, (3) a eutectic reaction, and (4) a solid–solid
combustion synthesis occurs. During the cooling period,
Eqs. (5) a solid solution reaction, (6) a hydriding reac-
tion, and (7) a modification transformation occurs. The
Mg2 NiH4 is formed from the hydriding of Mg2 Ni fol-
lowing the combustion synthesis of Mg2 Ni and before
the combustion synthesis of Mg2 Ni, the hydriding of
magnesium. The dehydriding of MgH2 then occurs.
A very significant phenomenon is that the volume
of sample substantially changed during the hydriding and
dehydriding reactions. Ono [15] reported results of the
volume expansions of the crystal cells from XRD data
of the reactions of magnesium to MgH2 , Mg2 Ni to high-
temperature Mg2 NiH4 , and the high- to low-tempera-
ture Mg2 NiH4 . These are 30.4% (0.2%) at 3408 C, 27.8%
Production of Hydrogen Storage Alloy of Mg2NiH4 11

Fig. 4. XRD patterns of samples in hydriding combustion synthesis of Mg2 NiH4 by heating to 873 K and maintaining at this temperature for 30
min. This was followed by cooling to 680 K and maintaining at this temperature for 30 min in 4.0 MPa hydrogen.

Table I. Compressed Pressure of Samples Used in Hydriding Table II. Ono’s Results of the Volume Expansions of the Crystal
Combustion Synthesis of Mg2 NiH4 Cells from XRD Data of Powdera,b

Sample no. Sample shape Compressed pressure (MPa) Reaction Volume expansion

1 Compressed cylinder 1100 Mg to MgH2 30.4% (0.2%), at 3408 C

2 Compressed cylinder 550 Mg2 Ni to Mg2 NiH4 (HT) 27.8% (0.2%), at 3208 C
3 Compressed cylinder 280 Mg2 NiH4 (HT) to Mg2 NiH4 (LT) 0.3% (0.1%), at 2348 C
4 Compressed cylinder 140
a From Ref. [15].
5 Powder 0
b The standard deviations are given in parentheses.

(0.2%) at 3208 C, and 0.3% (0.1%) at 2348 C (the stan-
dard deviations are shown in parentheses), respectively,
as presented in Table II. All of these volume expansions
inevitably occurred in our samples during the hydriding
combustion synthesis of Mg2 NiH4 .
We also measured the size of the cylinders before
and after the hydriding combustion synthesis. As given
in Table III, the height of sample 1 changed 49.1%
(almost 50%), which was in the highest compressive
pressure of 1100 MPa. It is 44.2% for sample 2, 34.4%
for sample 3, and 27.7% for sample 4. The trend is that
the higher the compressive pressure, the larger the height
change of the cylinder. The diameters of these cylin-
ders were not measured after synthesis because the small
width of the ceramic boat deformed them. However, it is
easy to observe, from Fig. 3, that the trend of the expan-
sion in diameter is the same as the height. From this
result, we consider that after synthesis the volumes of
the four cylinders are very similar.
Since the volume expansion of magnesium to MgH2
is so significant (30.4% as reported by Ono [15]), the
original particles of magnesium must be cracked and
very greatly enlarged. The cylinder must have already
changed to a very porous bulk before the hydriding reac-
12
Table III. Heights of the Compressed Cylinders before and after
Synthesis
Sample No. 1 2 3 4
Green pellet (mm) 8.05 8.60 9.60 10.80
Product (mm) 12.00 12.40 12.90 13.80
Increase (mm) 3.95 3.80 3.30 3.00
Change (%) 49.1 44.2 34.4 27.7
tion of Mg2 NiH4 , regardless of how high the compres-
sive pressure was. That is, all of the cylinders were in the
same condition (very porous bulk and ease to hydride)
when the hydriding reaction of Mg2 NiH4 occurred.
Figure 5 contains SEM images of samples 2(a)
and 5(b) after hydriding combustion synthesis. There are
very significant differences in particle size and surfaces
between the two images. Compared with sample 2, when
the compressed cylinder was used, sample 5 has much
larger and much more uniform particles when the pow-
der was used. Moreover, particles of sample 5 have a
very smooth skin, but the particles of sample 2 have a
very rough skin. Both of the particles in these samples
are irregular in shape.
It should be noted that, from Fig. 5b, the particles
not only have a smooth skin but also an aggregated bulk,
with a number of well-connected tunnels. The smooth
skin of the particle clearly is evidence that the parti-
cle must have undergone a process of melting. Actually,
the eutectic reaction of Mg–Ni system occurred in the
heating period at 779 K. Therefore, it is deduced that
the smooth skin of the particles and the well-connected
tunnels resulted from shrinkage of the magnesium parti-
cles during the eutectic reaction. When the metal pow-
der mixture was used, the particles contacted each other
in a stacked condition, without any strains and stresses.
The smooth skin of the particles, from the shrinkage, and
the state of aggregated bulk with a number of well-con-
nected tunnels remained during the later hydriding reac-
tions of Mg2 NiH4 .
The eutectic reaction of the Mg–Ni system, fol-
lowed by shrinkage of particles, which occurred in the
cylinder, is shown in sample 2. Due to the large stresses
and strains between and inside the particles, resulting
from the compressive pressure, the smooth skins of the
particles (from the shrinkage) were already destroyed
during subsequent reactions. Moreover, the particle size
became much smaller and a very rough surface devel-
oped, as shown in the SEM image of Fig. 5a.
The smooth skin of sample 5 particles in the SEM
image of Fig. 5b gives visible evidence of an eutectic
Li, Akiyama, and Yagi
reaction occurring in the hydriding combustion synthe-
sis of Mg2 NiH4 . In fact, a liquid phase often occurred,
which was necessary to conduct solid–solid combus-
tion synthesis. This is usually caused by the low-melting
point component, which acts as a trigger to the combus-
tion synthesis or self-propagation high-temperature syn-
thesis (SHS) [16]. This kind of liquid phase remained in
our system for only a few minutes. This is based on pre-
vious results on the reaction mechanism of the hydriding
combustion synthesis of Mg2 NiH4 [10]. A pure product
of Mg2 NiH4 , without any raw materials of magnesium
and nickel, persisted, as shown in Fig. 4, indicating that
the eutectic reaction played a very significant role in the
combustion synthesis of Mg2 Ni. In addition, it is very
effective for the nickel, of the high-melting component,
to diffuse homogeneously in the particle of magnesium,
even when the particles of magnesium and nickel were
only in a stacked condition.
CONCLUSION
In a study of the laboratory-scale production pro-
cess of the hydriding combustion synthesis of Mg2 NiH4 ,
the cylinders in different compressed pressures and the
powder mixture of the metals were used as raw material.
The results on pure Mg2 NiH4 indicated that there
was no significant effect of the compressive pressure on
the final products from observations of phase composi-
tion by XRD. Using this process, the hydrogen storage
alloy of Mg2 NiH4 can be simply obtained directly from
the powder mixture in stacked condition without using
compressive treatment. The microstructure of the prod-
uct of the powder differs from that of the product of
the compressed cylinders. From powder, there are larger
and smooth-skinned particles and an aggregated bulk
with well-connected tunnels. From the cylinder, there are
small size and rough-surfaced particles and a very porous
bulk. These results suggest a possibility of a new pro-
duction system for Mg2 NiH4 by hydriding combustion
synthesis, with many benefits including: simple pretreat-
ment, simple equipment, short operating time, high-qual-
ity product, and energy savings.
ACKNOWLEDGMENTS
This research was partially supported by the Min-
istry of Education, Science, and Culture, Japan (Grant
No. B-09450276 and 10450282). The authors would like
Production of Hydrogen Storage Alloy of Mg2NiH4 13

Fig. 5. SEM images of Mg2 NiH4 obtained by method of hydriding combustion synthesis from mixture of magnesium and nickel. (a) Compressed
cylinder at 550 MPa; (b) powder.
14
to thank Prof. R. Takahashi and Dr. X. H. Zhang (Insti-
tute for Advanced Materials Processing, Tohoku Univer-
sity) for their help in the experiment.
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