Journal of Alloys and Compounds 337 (2002) 148–154 L

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Hydrogen storage properties of ZrMnFe 12x Ni x (x50.2, 0.4, 0.5 and 0.6)
alloys
N. Mani, R. Sivakumar, S. Ramaprabhu*
Alternate Energy Technology and Magnetism and Magnetic Materials Laboratory, Indian Institute of Technology Madras, Chennai 600 036, India
Received 6 September 2001; accepted 25 October 2001

Abstract

Hydrogen absorption pressure–composition isotherms have been investigated for the ZrMnFe 12x Nix (x50.2, 0.4, 0.5 and 0.6) alloys
having the C14 type hexagonal structure in the temperature and pressure ranges 30#T #1008C and 0.1#P#40 bar using a pressure
reduction method. Powder X-ray diffractograms show that the lattice constants and the unit cell volume of ZrMnFe 12x Nix (x50.2, 0.4, 0.5
and 0.6) alloys decrease with increasing Ni content. The P–C isotherms show the presence of a single plateau region (a1b) in the
temperature and pressure ranges studied and it was found that the plateau pressure and plateau slope at any given temperature increase
with increasing Ni content except for ZrMnFe 0.5 Ni 0.5 , where the plateau slope is found to be small due to the atomic ordering in the alloy
due to presence of Fe and Ni in a 1:1 molar ratio. The desorption isotherms of ZrMnFe 0.5 Ni 0.5 at 30 and 508C show that the hysteresis is
very small. The dependence of the thermodynamics of dissolved hydrogen in ZrMnFe 12x Ni x –H (x50.2, 0.4, 0.5 and 0.6) systems in the
temperature range 30–508C on the hydrogen concentration have shown the existence of a, a1b and b phase regions as seen in the
isotherms. The powder X-ray diffractograms of the alloy hydrides show that these alloys do not undergo a structural transformation upon
hydrogenation. In ZrMnFe 0.5 Ni 0.5 , the kinetics of hydrogen absorption during activation and after several cycles at 308C have been
studied and compared.  2002 Elsevier Science B.V. All rights reserved.

Keywords: Transition metal compounds; Hydrogen absorbing materials; Gas–solid reaction; Kinetics

1. Introduction
Zirconium-based C14 Laves phase AB 2 alloys have
been the focus of attention recently due to their potential as
hydrogen storage materials and electrode materials for
Ni–MH batteries [1,2]. They have remarkable hydrogen
storage characteristics and their hydrogen storage prop-
erties can be significantly modified by an alloying pro-
cedure in which Zr is partially replaced by other suitably
chosen elements. ZrMn 2 has an excellent hydrogen storage
capacity but its desorption properties are quite poor, and
this hydrogen desorption capacity can be increased by a
partial substitution of other elements for Mn. Recently,
hydrogen storage properties in Zr-based Laves phase C14
alloys have been studied in order to investigate their
suitability for Ni–MH batteries [3,4].
The two C14 Laves phase alloys used in different
projects of technical scale are ZrMnFe and
*Corresponding author. Tel.: 191-44-445-8680; fax: 191-44-235-
0509.
E-mail address: ramp@mmm.iitm.ernet.in (S. Ramaprabhu).
Zr 0.02 Ti 0.98 V0.43 Cr 0.05 Mn 1.5 Fe 0.08 . ZrMnFe has an excel-
lent hydrogen intake capacity and fast kinetics but the
decrepitation upon hydrogenation in this alloy is very
large. Besides, the desorption plateau pressure at 258C is
well below 1 bar with a large plateau slope [5]. In
Zr 0.02 Ti 0.98 V0.43 Cr 0.05 Mn 1.5 Fe 0.08 , the kinetics of the hy-
drogen absorption is very fast, quite suitable for tech-
nological application with excellent cyclic stability. How-
ever, the disadvantages of this alloy are that the plateau
pressure is around 10 bar at 208C with large plateau slope
[6]. From the study of the hydrogen storage properties in
the C15 Laves phase Zrx Ho 12x Fe 2 (x501, 0.2, 0.3) and
the rhombohedral Zrx Tb 12x Fe 3 (x50.1, 0.2, 0.3) alloys, it
has been observed in our laboratory that the substitution of
Co for the Fe site in these alloys in the molar ratio of 1:1
remarkably reduces the plateau slope due to an increase in
the atomic order [7,8]. Based on these findings, in the
present work it has been planned to study the hydrogen
storage properties of Zr-based C14 Laves phase
ZrMnFe 12x Ni x (x50.2, 0.4, 0.5 and 0.6) alloys in the
ranges 0.1#P#40 bar and 30#T #1008C using high-pres-
sure apparatus based on the Sieverts method in order to

0925-8388 / 02 / $ – see front matter  2002 Elsevier Science B.V. All rights reserved.
PII: S0925-8388( 01 )01931-4
 N. Mani et al. / Journal of Alloys and Compounds 337 (2002) 148 – 154 149

find the influence of Ni on the hydrogen storage properties,

especially on the plateau slope when Ni and Fe are in a 1:1
molar ratio.

2. Experimental details

2.1. Sample preparation and powder X-ray diffraction

ZrMnFe 12x Ni x (0.2, 0.4, 0.5 and 0.6) alloys were

prepared in an arc furnace under an argon atmosphere.
They were melted in stoichiometric proportions. A 6 wt.%
of excess of Mn was added to the total mixture following
the normal procedure since the vapour pressure of Mn is
very high. The alloys buttons were remelted several times
by turning them over to ensure homogeneity. The weight
loss of the sample during their preparation was less than
0.7%. Since the as-formed alloys showed the formation of
a single phase, no annealing treatment was given. The
X-ray powder diffraction patterns were taken with Fe K a
radiation.

2.2. Hydrogen absorption–desorption isotherms and

kinetics studies

Hydrogen absorption pressure–composition–tempera-

ture (PCT) relationship and kinetics data were collected by
a conventional gaseometric technique. An apparatus based
on the pressure reduction method and operating in the
temperature range 30–3008C and in the pressure range
0.1–100 bar was employed [9]. Prior to the measurements,
the hydrogen absorption system was flushed with hydrogen
several times and evacuated each time to 10 26 Torr. The
data were collected after activating the samples by several
hydriding and dehydriding cycles at a pressure of 20 bar
and 1008C. Following each experiment, the sample was
degassed at 2008C under a vacuum of 10 26 Torr. The
kinetics data were collected by recording the change in
pressure as a function of time at constant temperature.
Fig. 1. Powder X-ray diffractograms of the alloys ZrMnFe 12x Ni x –H
(x50.2, 0.4, 0.5 and 0.6) with Fe K a radiation.
a, c and the unit cell volume were evaluated using a least
square refinement technique and are listed in Table 1. The
dependence of the cell constants and volume of the unit
cell on the Ni content in ZrMnFe 12x Ni x is shown in Fig. 2.
The lattice constants and the unit cell volume of
ZrMnFe 12x Ni x decrease with increasing Ni content due to
the smaller atomic radius of Ni compared to Fe.

3.2. P–C isotherm

3. Results and discussion
The P–C isotherms measured for the system
3.1. Crystal structure ZrMnFe 12x Ni x (x50.2, 0.4, 0.5 and 0.6) in the ranges

ZrMnFe 12x Ni x (x50.2, 0.4, 0.5 and 0.6) crystallizes in Table 1

the C14 hexagonal structure (space group P63 /mmc) as The lattice parameters, the unit cell volume and the average number of
confirmed from the powder X-ray diffraction studies taken outer electrons in ZrMnFe 12x Ni x alloys
with Fe K a radiation at room temperature (Fig. 1). Since Alloy ˚
a (A) ˚
c (A) ˚ 3
v (A) 2DV /V (%) ANOE
the changes in the unit cell parameters are very small, the
ZrMnFe 5.011 8.202 178.4 – 6.33
lattice parameters have been precisely obtained using Si as ZrMnFe 0.8 Ni 0.2 5.008 8.196 178.0 0.22 6.46
the standard by mixing Si with the alloys while taking the ZrMnFe 0.6 Ni 0.4 5.008 8.182 177.7 0.39 6.60
diffractograms. The average number of outer electrons ZrMnFe 0.5 Ni 0.5 5.004 8.174 177.3 0.62 6.66
(ANOE) in these alloys is less than seven indicating the ZrMnFe 0.4 Ni 0.6 4.998 8.167 176.7 0.95 6.73
preference for the formation of the C14 structure (Table ˚
The values of a and c are with an accuracy of 0.003 and 0.006 (A),
1). In the hexagonal representation, the lattice parameters, respectively.
150 N. Mani et al. / Journal of Alloys and Compounds 337 (2002) 148 – 154
Fig. 2. The variation of unit cell constants and volume with Ni con-
centration in ZrMnFe 12x Ni x –H (x50.2, 0.4, 0.5 and 0.6) system.
30#T #1008C and 0.1#P#40 bar are shown in Figs. 3–6,
respectively. These isotherms indicate that there are two
single phase (a and b) regions and one mixed phase (a1b)
region in the temperature and pressure ranges studied. The
Fig. 3. Hydrogen absorption isotherms of ZrMnFe 0.8 Ni 0.2 .
Fig. 4. Hydrogen absorption isotherms of ZrMnFe 0.6 Ni 0.4 .
Fig. 5. Hydrogen absorption isotherms of ZrMnFe 0.5 Ni 0.5 .
maximum hydrogen concentration was found to be around
3.4 hydrogen atoms per formula unit at 30 bar and 308C in
ZrMnFe 0.5 Ni 0.5 . At any particular temperature, the plateau
pressure Pa→b increases with the increase in Ni content
due to the contraction of the unit cell volume (see Tables 1
and 2). The plateau slope also increases with the increase
in x Ni except for ZrMnFe 0.5 Ni 0.5 , wherein the plateau
slope is less (Table 2), which can be attributed to the
increase in the atomic order of the alloy due to the
presence of Fe and Ni in the molar ratio 1:1.
The hydrogen absorption studies on LaNi 5 and its
substitutes showed that the plateau pressure depends
exponentially on the volume of the unit cell of the alloys
[10,11]. Fig. 7 gives the dependence of the plateau
pressure at 30 and 508C on the unit cell volume of
ZrMnFe 12x Ni x . At any particular temperature, Pa→b in
ZrMnFe 12x Ni x (x50.2, 0.4, 0.5 and 0.6) increases with an
increase in x Ni due to the increase in the strain energy
necessary to accommodate the hydrogen atoms in the
interstitial sites. The desorption isotherm of
ZrMnFe 0.5 Ni 0.5 at 30 and 508C (Fig. 8) show that the
Fig. 6. Hydrogen absorption isotherms of ZrMnFe 0.4 Ni 0.6 .
 N. Mani et al. / Journal of Alloys and Compounds 337 (2002) 148 – 154 151

Table 2
The equilibrium pressure, plateau slope, DHH , DSH and DmH in ZrMnFe 12x Ni x –H systems
Alloy Equilibrium Plateau 2DHH 2DSH 2DmH
pressure (bar) slope a (kJ / mol H) (J / K / mol H) (kJ / mol H)
308C 508C 308C 508C
ZrMnFe 0.8 Ni 0.2 3.5 7.0 1.12 14.44 52.83 1.57 2.61
ZrMnFe 0.6 Ni 0.4 3.6 8.0 1.71 16.81 60.73 1.61 2.80
ZrMnFe 0.5 Ni 0.5 4.2 9.0 0.96 15.50 57.13 1.81 2.95
2.3 b 5.4 b 0.66 b 17.36 c 60.76 c 1.05 b 2.26 b
ZrMnFe 0.4 Ni 0.6 4.5 9.4 1.73 14.98 55.71 1.89 3.01
a
ln sPH / M 52.5 /PH / M 50.5d.
b
Desorption values.
c
DH dplat and DS dplat .

3.3. Thermodynamics of dissolved hydrogen

The relative partial molar enthalpy (DHH ) and relative

partial molar entropy (DSH ) of dissolved hydrogen in
ZrMnFe 12x Ni x –H can be obtained at any particular con-
centration of hydrogen from the van’t Hoff equation [12]:

Fig. 7. The variation of plateau pressure (Pa→b ) with unit cell volume in
ZrMnFe 12x Ni x –H.
hysteresis is very small with a free energy loss per cycle of
DGloss 5]12 RT ln(Pa /Pd )50.76 and 0.69 kJ / mol H at 30 and
508C, respectively. This energy is dissipated through the
surroundings as heat and provides the total entropy pro-
duction per cycle. Table 2 shows the hydrogen absorption–
desorption capacities, equilibrium pressures (Pa and Pd )
and plateau slope for these systems studied along with the
hysteresis for ZrMnFe 0.5 Ni 0.5 .
S
DHH DSH
ln PH 2 5 2 ]] 2 ]]
RT R
D
DHH and DSH of the dissolved hydrogen for a particular
R value are obtained by a least squares technique from the
slope and intercept of a ln PH 2 and (1 /T ) plot, respective-
ly. The dependence of these parameters on the hydrogen
concentration in ZrMnFe 12x Ni x –H (x50.2, 0.4, 0.5 and
0.6) is shown in Figs. 9–12. Since in an alloy–hydrogen
system, the heat of formation is different for single and
two phase regions, the variation of DHH and DSH as a
function of the hydrogen concentration is useful for the
identification of different phases and the phase boundaries.
Figs. 9–12 show the presence of the different phases a,
(a1b) and b as seen in the isotherms: DH a→b H and DS Ha→b
for ZrMnFe 12x Ni x –H (x50.2, 0.4, 0.5 and 0.6) in the
range 30–508C. The Gibb’s free energy (DmH 5DHH 2
d d
TDSH ) at 30 and 508C along with DH plat and DS plat are

Fig. 9. The variation of DHH and DSH with hydrogen concentration in

Fig. 8. Hydrogen desorption isotherms of ZrMnFe 0.5 Ni 0.5 . ZrMnFe 0.8 Ni 0.2 –H.
152 N. Mani et al. / Journal of Alloys and Compounds 337 (2002) 148 – 154
Fig. 10. The variation of DHH and DSH with hydrogen concentration in
ZrMnFe 0.6 Ni 0.4 –H.
Fig. 11. The variation of DHH and DSH with hydrogen concentration in
ZrMnFe 0.5 Ni 0.5 –H.
listed in Table 2. Fig. 13 shows the dependence of DmH on
the unit cell volume of the alloys which suggests that the
strain energy necessary to accommodate the interstitial
Fig. 12. The variation of DHH and DSH with hydrogen concentration in
ZrMnFe 0.4 Ni 0.6 –H.
Fig. 13. The variation of DmH with unit cell volume in ZrMnFe 12x Ni x –H
systems.
hydrogen increases with the decrease of the size of these
interstitial sites in virtue of the decrease in the unit cell
volume.
3.4. X-ray diffractograms of alloy hydrides
It is known that AB 5 alloys such as SmCo 5 and PrCo 5
change their structure from hexagonal CaCu 5 to an ortho-
rhombic structure upon hydrogenation whereas, AB 3 alloys
such as TbFe 3 , YFe 3 and ErFe 3 retain their PuNi 3 structure
upon hydrogenation [13–15]. Further, studies on
Zr x Tb 12x Fe 3 –H have shown that these alloys do not
transform upon hydrogenation [16]. The powder X-ray
diffractograms of the present alloy hydrides show that
there is no structural change upon hydrogenation. For
example, the powder X-ray diffractograms for
ZrMnFe 0.5 Ni 0.5 –H y [y51.61 (a1b) and 2.91 (b)] taken
with Fe K a radiation at room temperature are shown in
Fig. 14. It can be seen that the diffraction pattern for the
hydride in the b phase is identical to that of the parent
alloy with an increase in the unit cell volume. For the
mixed (a1b) phase, the diffraction pattern shows two sets
of Bragg reflections, each one corresponding to the a and
b phase component of the alloy hydride (Table 3). Thus,
there is only volume expansion upon hydrogenation up to
about 19.5% without any change in the crystal structure.
3.5. Kinetics of hydrogen absorption
The hydrogen absorption kinetics during activation in
these alloys at an initial pressure of around 30 bar suggests
that the kinetics of absorption was easy with the increase
in Ni content. Fig. 15 shows the kinetics of absorption at
308C in ZrMnFe 0.5 Ni 0.5 during activation and after several
cycles of absorption–desorption with an initial pressure of
26.9 and 31.96 bar, respectively. Fig. 15 suggests that
hydrogen absorption is quite fast even during activation,
 N. Mani et al. / Journal of Alloys and Compounds 337 (2002) 148 – 154 153

requiring less than 20 min for attaining the equilibrium

pressure.

4. Conclusion

Hydrogen absorption P–C isotherms of ZrMnFe 12x Ni x –

H (x50.2, 0.4, 0.5 and 0.6) and the desorption isotherm of
ZrMnFe 0.5 Ni 0.5 –H have been investigated in the tempera-
ture and pressure ranges 30#T #1008C and 0.1#P#40
bar. This study revealed that the partial substitution of Ni
for Fe in ZrMnFe decreases the unit cell volume with the
increase in Ni content. This results in an increase of the
plateau pressure and the plateau slope with the exception
of ZrMnFe 0.5 Ni 0.5 wherein the plateau slope is smaller,
which can be attributed to the increase in the atomic order
of the alloy due to the presence of Fe and Ni in the molar
ratio 1:1. The different phases are identified by the
variation in DHH and DSH with hydrogen concentration
which is confirmed by the powder X-ray diffraction of the
alloy hydrides at the appropriate concentrations. The
powder X-ray diffractograms of the alloy hydrides show
that these alloys do not undergo structural transformation
upon hydrogenation. The kinetics of absorption in these
alloys are quite fast even at room temperature during
activation.

Fig. 14. Powder X-ray diffractograms of ZrMnFe 0.5 Ni 0.5 and

ZrMnFe 0.5 Ni 0.5 –H y [y51.61 (a1b) and 2.91 (b)] with Fe K a radiation.
Acknowledgements
Table 3
The lattice parameters, the unit cell volume and the volume expansion in The authors are grateful to the MNES and CSIR funding
the hydrides of ZrMnFe 0.5 Ni 0.5 agencies for supporting this work. N.M. is grateful to IIT
Alloy ˚
a (A) ˚
c (A) ˚ 3
v (A) DV /V (%) Madras for financial support.
ZrMnFe 0.5 Ni 0.5 5.004 8.174 177.3 –
ZrMnFe 0.5 Ni 0.5 H 1.61 (a) 5.002 8.176 177.2 –
(b) 5.131 8.582 195.6 10.3
ZrMnFe 0.5 Ni 0.5 H 2.91 (b) 5.236 8.928 211.9 19.5 References

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