Electrochimica Acta 54 (2009) 13831387

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Study on kinetics and electrochemical properties of low-Co AB5 -type alloys for
high-power Ni/MH battery
Wencui Zhang b , Shumin Han a,b, , Jiansheng Hao a , Yuan Li b , Taoyu Bai b , Jingwu Zhang a
a
b

State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, PR China
College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, PR China

a r t i c l e

i n f o

Article history:
Received 26 June 2008
Received in revised form 9 September 2008
Accepted 11 September 2008
Available online 19 September 2008
Keywords:
Hydrogen storage alloys
Rare earth Ce
Kinetics
Electrochemical properties
High-power Ni/MH batteries

a b s t r a c t
The structure and electrochemical kinetics properties of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30
(x = 0.10, 0.20, 0.30, 0.40, 0.50) hydrogen storage alloys have been investigated. XRD shows that the alloys
consist of LaNi5 phase with hexagonal CaCu5 structure. With increase in Ce content, the parameter a and
cell volume decrease remarkably, but the parameter c increases slightly. The limiting current density IL
and the hydrogen diffusion coefcient D increase, and the exchange current density I0 increases rstly
from 201.4 mA/g (x = 0.10) to 277.9 mA/g (x = 0.30) and then decreases to 208.5 mA/g (x = 0.50). Meanwhile,
high rate dischargeability (HRD) at 1440 mA/g increases from 44.1% (x = 0.10) to 59.9% (x = 0.30), and then
decreases to 44.2% (x = 0.50). As the amount of Ce increases, the plateau pressure of PC isotherms increases
gradually, the capacity retention of the alloys increases rstly and then decreases, the alloy with x = 0.30
has the higher capacity retention and cycling stability, but the maximum discharge capacity of alloys
decreases. Ce is a vital element in favor of kinetics properties of rare earth-based AB5 -type alloys, and the
substitution of La with Ce in suitable amount could improve the HRD by increasing kinetics.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Nickel/metal hydride (Ni/MH) secondary batteries using AB5 type hydrogen storage alloys as negative electrode materials have
been widely used in portable electric devices and power sources
due to their high energy density, environmental friendliness and
interchangeability with nickel/cadmium batteries. But in very
recent years, Ni/MH battery is encountering serious competition
from Li-ion batteries and other advanced secondary batteries. It is
more and more urgent to reduce production cost and improve specic power of Ni/MH batteries to enhance their competition and
extend their application in high-power elds, for example, hydride
electric vehicles, power tools and so on. Therefore, it is still imperative to improve high-rate capacity of rare earth-based AB5 -type
alloys to meet further requirements of high-power Ni/MH batteries.
For improving discharge performance of rare earth-based AB5 type alloys at high discharge current density, many researches,
especially the partial replacement of La with Ce, Pr, Nd, Mg, Li,
Ca and Ni with Fe, Al, Sn, etc. have been conducted and studied extensively [15]. Among them, the partial substitution of Ce

Corresponding author at: College of Environmental and Chemical Engineering,

Yanshan University, Qinghuangdao 066004, China. Tel.: +86 335 8061569;
fax: +86 335 8061569.
E-mail address: hanshm@ysu.edu.cn (S. Han).
0013-4686/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2008.09.019

for La has been proved effective. Tan et al. [6] studied the performances of La1x Cex Ni5 alloys by powder microelectrode, and
pointed out that the partial substitution of La with Ce could improve
discharge potential of La1x Cex Ni5 alloys, the activity of electron
transfer reaction on the alloy surface and the hydrogen diffusion coefcient in the bulk of alloy. Ye et al. [7] reported that
increase in Ce and decrease in La improved high-rate capacity
of ReNi3.55 Co0.75 Mn0.40 Al0.30 alloys, and ascribed improvement of
HRD to lower hydride stability. Moreover, the investigation on
LaMgNi type alloy electrodes also showed that, substitution of La
by Ce caused increase in hydrogen absorption/desorption plateau
pressure and improved cycling life, HRD and exchange current density (I0 ) [8,9]. Whereas, research of Ce on the kinetics of low-Co
AB5 -type alloys used as negative electrode materials for highpower batteries and the mechanism has been few so far.
In order to improve high-rate capacity, reduce cost and explore
effect of Ce on electrochemical characteristics, a series of low-Co
AB5 -type alloys with different amount of Ce were prepared. The
structure and electrochemical kinetics of the alloys were investigated systematically in this paper.

2. Experimental
La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 (x = 0.10, 0.20,
0.30, 0.40, 0.50) alloys were prepared by inductive melting La, Ce,

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W. Zhang et al. / Electrochimica Acta 54 (2009) 13831387

Table 1
Lattice parameters of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 alloys.
Sample (x)

Phases

Lattice constants
a ()

c ()

0.10
0.20
0.30
0.40

LaNi5
LaNi5
LaNi5
LaNi5

5.045
5.036
5.017
5.008

4.043
4.050
4.051
4.052

c/a

Cell volume (3 )

0.802
0.804
0.807
0.809

89.11
88.95
88.30
88.02

Pr, Nd, Ni, Co, Mn and Al (purity 99.5%) under argon atmosphere.
Then the ingots were annealed at 1173 K for 6 h. The chemical composition was nally examined by ICP analysis. The prepared ingots
were mechanically crushed and ground in the air into ne powders.
Powders of 200300 mesh were used for electrochemical properties measurement and those below 300 mesh for XRD analysis.
The XRD patterns were obtained on a D/Max-2500/PC X-ray
diffractometer (Cu K radiation) and analyzed using Jade-5.0 software.
The electrode preparation method is as reported in our previous paper [10]. The test electrodes were prepared by cold pressing
a mixture of 0.15 g alloy powders and 0.75 g carbonyl nickel powders into a pellet of 10 mm in diameter under 20 MPa. The kinetics
and electrochemical measurements were performed at 298 K in a
standard tri-electrode system, consisting of metal hydride (MH)
working electrode, sintered Ni(OH)2 /NiOOH counter electrode and
Hg/HgO reference electrode with 6 mol/L KOH solution as electrolyte. During discharge capacity and cycle life tests, the electrodes
were fully charged (the over-charged ratio was approximately 50%)
at current density of 72 mA/g followed by 10 min rest, and then discharged at the same current density to cut-off potential of 0.6 V
(vs. Hg/HgO). The high rate dischargeability (HRD) was measured
at different discharge current densities (Id ), and the HRD is dened
and calculated according to the following formula:
HRD(%) =

Cd
100
C72

where Cd and C72 are the discharge capacity at Id mA/g and 72 mA/g,
respectively.
The pressurecomposition isotherms (PC) were obtained
through an electrochemical method. The fully charged electrodes
were discharged for 0.5 h, followed by 0.5 h rest. The equilibrium
potential was recorded and converted to equilibrium pressure of
hydrogen on the basis of Nernst equation [11]:

Eeq vs.

Hg
HgO

Fig. 1. XRD patterns of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 alloys.

that with the increase in Ce content, the parameter a and cell volume decrease remarkably, but the parameter c increases slightly,
which agrees well with the result reported by Yuan et al. [12] in the
study of La0.8(1x) Ce0.8x (PrNd)0.20 Ni3.55 Co0.75 Mn0.40 Al0.30 alloys
and Tan et al. [6] in the study of La1x Cex Ni5 alloys. It can also be
found that the cell volume decreases linearly as x increases. The
relationship of cell volume vs. Ce content can be described as the
following equation:
V (cell volume) = (89.575 3.92x)

The shrinkage of unit cell with high Ce content can be ascribed

to its particular electron structure 4f1 5d1 6s2 , which causes that
Ce element often has two contributions (Ce3+ , Ce4+ ) resulting in
smaller average atomic radius of Ce (1.73 ) than that of La (1.87 )
[13]. Moreover, the anisotropic changes in lattice parameters can
be attributed to lack of symmetry in 4f orbit of Ce atoms.
3.2. PC isotherms
The
electrochemical
desorption
PC
isotherms
of
La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30
(x = 0.10,
0.20,
0.30, 0.40) alloy electrodes are shown in Fig. 2. It can be clearly
noticed that the electrodes have at and long plateau except that

= 0.925 0.030 log(peq )

The linear polarization and the anode polarization curves were

measured on ZF-9 potentiostat by scanning electrode potential at
the rate of 5 mV/min and 5 mV/s from 5 to 5 mV and from 0 to
1500 mV (vs. open circuit potential) at 50% depth of discharge,
respectively. As for the potential static step discharge, the electrodes were in fully charged state, and discharged at +500 mV
potential steps for 3600 s on the same ZF-9 potentiostat.
3. Results and discussion
3.1. Phase structure
Fig.
1
shows
the
XRD
patterns
of
(x = 0.10,
0.20,
La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30
0.30, 0.40) alloys. It can be seen that all the alloys consist of hexagonal CaCu5 -type structure LaNi5 phase, though intensities of the
characteristic peaks are slightly different from each other. The calculated values of cell parameters are listed in Table 1. It is obvious

Fig.
2. Electrochemical
desorption
PC
isotherms
La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 alloy electrodes.

for

W. Zhang et al. / Electrochimica Acta 54 (2009) 13831387

Fig. 3. Linear polarization curves of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30
alloy electrodes.

with x = 0.40. The plateau pressure increases as x increases, which

indicates decreasing hydride stability. The alloy with x = 0.30 has
atter plateau than the others, and when x increases to 0.40, the
equilibrium pressure increases sharply and the plateau becomes
sloppier. In general, the hydrogen desorption pressure is directly
related to unit cell volume of alloys [14]. The decrease in unit
cell volume results in increase of plateau pressure for hydrogen
desorption.
3.3. Kinetics characteristics
The exchange current density (I0 ) is used to characterize electrocatalytic activity for charge-transfer reaction on surface of
the alloy electrode. Fig. 3 shows linear polarization curves of
La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 (x = 0.10, 0.20, 0.30,
0.40, 0.50) alloy electrodes. Polarization resistance Rp can be
obtained from Fig. 3, and consequently exchange current density
I0 can be calculated according to the equation [15]:
I0 =

1385

Fig. 4. Anode polarization curves of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30
alloy electrodes.

of overpotential and reaches a maximum, which is dened as

limiting current density IL . The IL can be related to diffusion rate
of hydrogen in the alloy [16,17]. The limiting current densities
obtained increase from 2240 to 2793 mA/g as x increases from 0.10
to 0.40, which indicates that the hydrogen diffusion rate becomes
faster with increase in Ce content [18].
In addition, the hydrogen diffusion rate can also be
estimated by potential-step method. Fig. 5 illustrates correspondence of anodic current density to discharge time of
La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 (x = 0.10, 0.20, 0.30,
0.40) alloy electrodes at fully charged state and 298 K. It can be
seen that the semilogarithmic value of the anodic current (log i)
exhibits an approximately linear dependence on the time (t) for
a long time. In this case, the surface concentration of hydrogen
approaches zero, thus, the electrode reaction will be controlled

RT
FRp

where R is the gas constant (J/(mol K)), T the absolute temperature

(K) and F is the Faraday constant (C/mol). The results obtained are
listed in Table 2. It can be seen that the Rp value rst decreases
from 123.23 m (x = 0.10) to 89.28 m (x = 0.30) and then increases
to 123.16 m (x = 0.50). Consequently, I0 increases from 201.4 mA/g
(x = 0.10) to 277.9 mA/g (x = 0.30), and then decreases to 208.5 mA/g
(x = 0.50), which indicates the charge transfer rate increases from
x = 0.10 to x = 0.30 and then decreases.
The hydrogen diffusion rate in alloy bulk can be
characterized
by
anode
polarization
curve
measurement. Fig. 4 shows the anode polarization curves of
La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30
(x = 0.10,
0.20,
0.30, 0.40) alloy electrodes. During the anodic polarization process, it can be seen that the anodic current increases with increase

Fig. 5. Correspondence of anodic current density vs. discharge time of

La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 alloy electrodes.

Table 2
Electrochemical kinetics parameters of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 alloy electrodes.
Sample (x)

Polarization
resistance Rp (m)

Exchange current
density I0 (mA/g)

Limiting current
density IL (mA/g)

Hydrogen diffusion coefcient

D (1011 cm2 /s)

0.10
0.20
0.30
0.40

123.23
102.81
89.28
93.65

201.4
241.4
277.9
265.0

2240
2474
2678
2793

13.8
14.7
17.7
22.3

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W. Zhang et al. / Electrochimica Acta 54 (2009) 13831387

Table 3
Charge-discharge parameters of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 alloy
electrodes.

Fig. 6. HRD of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 alloy electrodes.

by hydrogen diffusion in the alloy bulk. The hydrogen diffusion

coefcient D in the bulk of the alloy can be calculated by the
following formula [19]:
log i = log

 6FD
da2

(C0 Cs )

2 D
t
2.303 a2

where i is anodic current density (mA/g), D the hydrogen diffusion

coefcient (cm2 /s), d the density of the alloy (g/cm3 ), a radius of
the alloy particle, C0 the initial hydrogen concentration in the bulk
of the alloy (mol/cm3 ), Cs the surface hydrogen concentration of
the alloy (mol/cm3 ) and t is the discharge time (s). Using that a is
13 m, D can be calculated according to the equation, and is summarized in Table 2. It can be seen that hydrogen diffusion coefcient
D of the alloys increases from 13.8 1011 to 22.3 1011 cm2 /s as
x increases from 0.10 to 0.40, which indicates that the hydrogen
diffusion rate in the alloy bulk increases with increasing content
and is in good agreement with the results of the anode polarization
measurements. It has been stated above that the decrease in cell
volume with increasing Ce content causes poorer hydride stability
as exhibited by higher plateau pressure in Fig. 2. So the increase in
hydrogen diffusion mainly originates from the rise of plateau pressure during hydrogen desorption process according to literature
[8,20].

Fig. 7. High rate dischargeability as a function of exchange-current density for

La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 alloy electrodes.

Sample (x)

Na

Cmax (mAh/g)

C1440 (mAh/g)

HRD1440 (%)

S100 (%)

0.10
0.20
0.30
0.40
0.50

4
4
3
4
4

356
353
349
347
345

156
166
208
186
147

44.1
47.4
59.9
53.9
44.2

86.2
88.4
89.1
88.5
87.5

The HRD is one of the key parameters for practical application of alloys as negative electrode materials of high-power
secondary Ni/MH batteries, which stands for overall kinetics properties. The HRD of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30
(x = 0.10, 0.20, 0.30, 0.40, 0.50) alloys at different current densities is
shown in Fig. 6. It can be seen that the HRD increases as x increases
from 0.10 to 0.30, and then decreases. At Id = 1440 mA/g, the discharge capacity increases from 156 mAh/g (x = 0.10) to 208 mAh/g
(x = 0.30) and then decreases to 147 mAh/g (x = 0.50), accordingly,
HRD1440 increases from 44.1% (x = 0.10) to 59.9% (x = 0.30) and then
decreases to 44.2% (x = 0.50).
Iwakura et al. [21] have shown that, if the electrochemical
reaction on the surface is the rate-determining factor, a linear
dependence of the high-rate dischargeability on the exchange current density should be observed. In contrast, if the diffusion of
hydrogen in the bulk is the rate-determining factor, the high-rate
dischargeability should be constant, irrespective of exchange density. Plot of HRD at 1080 mA/g vs. exchange current density is shown
in Fig. 7. It can be seen that HRD1080 shows a linear dependence on
I0 except for the point x = 0.20, which may be attributed to some
deviation during the measurement. The results above indicate that
charge-transfer process at the electrode surface is a more important
factor than hydrogen atoms diffusion process in the bulk.
3.4. Electrochemical properties
The cycle number needed for the electrodes to be activated (Na ) and the maximum discharge capacity (Cmax ) of
La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 (x = 0.10, 0.20, 0.30,
0.40, 0.50) alloy electrodes are tabulated in Table 3. It can be seen
that the alloys can be fully activated within 34 charge/discharge
cycles. But the maximum discharge capacity decreases from
356 mAh/g (x = 0.10) to 345 mAh/g (x = 0.50) with increasing x.
The decrease in maximum discharge capacity with increasing Ce

Fig.
8. Discharge
capacity
vs.
cycle
La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 alloy electrodes.

number

of

W. Zhang et al. / Electrochimica Acta 54 (2009) 13831387

content can be attributed to decrease in unit cell volume, which

would usually decrease the number of H-accommodating sites
because of the cell distortion.
Fig. 8 shows the relationship of discharge capacity vs. cycle number for La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30 (x = 0.10,
0.20, 0.30, 0.40, 0.50) alloy electrodes. It should be noted that the
capacity decreases differently with increase of cycle number. The
capacity retention used to represent the cycling stability can be
calculated by the following formula:
Sn (%) =

Cn
100
Cmax

where Sn is the capacity retention at n cycles, Cn the discharge

capacity at n cycles and Cmax is the maximum discharge capacity. The capacity retention at 100th cycle S100 is listed in Table 3. It
shows that S100 increases rstly and then decreases as increase in
x from 0.10 to 0.50, reaching a maximum at x = 0.30.
4. Conclusion
The effect of Ce on phase structure, kinetics and electrochemical properties of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30
(x = 0.10, 0.20, 0.30, 0.40, 0.50) hydrogen storage alloys were investigated systematically. XRD shows that the alloys have single-phase
CaCu5 -type structure. With increase in Ce content, the cell parameter a and the cell volume decrease, but cell parameter c and the
value of c/a increase. As x increases from 0.10 to 0.50, the limiting
current density IL and the hydrogen diffusion coefcient D increase,
the exchange current density I0 increases rstly from 201.4 mA/g
(x = 0.10) to 277.9 mA/g (x = 0.30) and then decreases to 208.5 mA/g
(x = 0.50), HRD at 1440 mA/g increases from 44.1% (x = 0.10) to 59.9%
(x = 0.30) and then decreases to 44.2% (x = 0.50). A linear dependence of HRD1080 on exchange current density can be found, which
suggests that hydrogen reaction on surface plays more important
role than hydrogen diffusion in alloy bulk. The capacity retention
of the alloys increases rstly and then decreases, the alloy with
x = 0.30 has the higher capacity retention and cycling stability, but
the maximum discharge capacity decreases with increase in Ce

1387

content. It can be summarized that Ce benets improvement in

HRD and kinetics of La0.90x Cex Pr0.05 Nd0.05 Ni3.90 Co0.40 Mn0.40 Al0.30
hydrogen storage alloys in some extension, the alloy with x = 0.30
has higher kinetics and exhibits better electrochemical properties.
Acknowledgements
This project is nancially supported by the National Natural
Science Foundation of China (20673093), the Natural Science Foundation of Hebei Province (B2007000303) and Support Program for
Hundred Excellent Innovation Talents from the Universities and
Colleges of Hebei Province.
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