J Solid State Electrochem (2014) 18:577–593
DOI 10.1007/s10008-013-2300-3
REVIEW
Kinetic and thermodynamic studies of hydrogen storage alloys
as negative electrode materials for Ni/MH batteries: a review
M. Tliha & C. Khaldi & S. Boussami & N. Fenineche &
O. El-Kedim & H. Mathlouthi & J. Lamloumi
Received: 7 February 2013 / Revised: 8 October 2013 / Accepted: 14 October 2013 / Published online: 19 November 2013
# Springer-Verlag Berlin Heidelberg 2013
Abstract This paper reviews the present performances of
intermetallic compound families as materials for negative
electrodes of rechargeable Ni/MH batteries. The performance
of the metal-hydride electrode is determined by both the
kinetics of the processes occurring at the metal/solution
interface and the rate of hydrogen diffusion within the bulk
of the alloy. Thermodynamic and electrochemical properties
for each hydride compound family will be reported. The steps
of hydrogen absorption/desorption such as charge-transfer
and hydrogen diffusion for evaluating the electrochemical
properties of hydrogen storage alloys are discussed. Exchange
current density (I 0) and hydrogen diffusion coefficient (D H)
are the two most important parameters for evaluating the
electrochemical properties of metal hydride electrode. The
values of the two parameters for a number of hydrogen storage
alloys are compared. The relationship between alloy
composition and electrochemical properties is noted and
evaluated.
M. Tliha (*) : C. Khaldi : S. Boussami : H. Mathlouthi :
J. Lamloumi
Laboratoire de Mécanique, Matériaux et Procédés, ESSTT,
Université de Tunis, 5 Avenue Taha Hussein, 1008 Tunis, Tunisia
e-mail: Mohamed.Tliha@esstt.rnu.tn
M. Tliha
Department of Physics, University College, Umm-Alqura University,
Al-Qunfudah, Saudi Arabia
N. Fenineche
IRTES-LERMPS/FR FCLAB, UTBM, Site de Sévenans,
90010 Belfort Cedex, France
O. El-Kedim
FEMTO-ST, MN2S, UTBM, Site de Sévenans,
90010 Belfort Cedex, France
Keywords Intermetallic compounds . Thermodynamic
properties . Electrochemical kinetics . Diffusion coefficient of
hydrogen . Exchange current density
Introduction
It is very important to develop electric vehicles for protecting
environment, saving energy, and improving energy structure.
With enhancement of consciousness of environment
protection and increasing exhaustion of oil resources,
countries and groups all over the world have drawn up
development projects of electric vehicles (EV) and hybrid
electric vehicles [1]. However, the final acceptance of electric
vehicles will depend strongly on the electrochemical
performances of the battery and on its acquisition price and
maintenance costs [2]. The nickel–metal hydride (Ni/MH) is
presently the most promising battery system for electric
vehicles in the short and mid-term, which has many
advantages, such as high energy density, high rate capacity,
good overcharge and overdischarge capability, and containing
no poisonous heavy metals and no electrolyte consumption
during charge/discharge cycling [3–9]. The rechargeable
nickel–metal hydride battery has a similar design to that of
nickel–cadmium system (Ni/Cd). The principal difference is
that the former uses hydrogen absorbed in a metal alloy for the
active negative material in place of cadmium in the latter
design. The active material of the positive electrode of the
Ni/MH battery is nickel oxy-hydroxide (NiOOH), in the
charged state. The negative active material in the charged state
is hydrogen, in the form of a metal hydride. The high-energy
density, excellent power density, and long cycle life of Ni/MH
batteries also make them a leading technology as the battery
power source for EVs, especially in bipolar designs.
578
Therefore, the development of Ni/MH batteries is one of
the most important areas of study on high-energy density
batteries today. Metal hydrides are regarded as promising
candidates for the negative materials of nickel/metal-hydride
(Ni/MH) batteries due to their high-energy density, favorable
charge and discharge ability, long charge–discharge cyclic
life, and environmental compatibility [5, 6, 10–16]. The most
important electrochemical characteristics of the hydrogen
storage compounds used in these batteries include capacity,
cycle life time, exchange current density, and equilibrium
potential. The electrochemical behavior of such intermetallics
depends on the types of intermetallics, microstructure, the
nature and amount of each element in the intermetallic
compound, and the electrochemical process (es) taking place.
These electrochemical characteristics can be altered by
designing the composition of the hydrogen storage alloy to
provide optimum performance of the Ni-MH batteries.
Different methods have been used to study the kinetics of
metal hydrides [17–27]. Electrochemical impedance
spectroscopy (EIS) has been a standard tool for investigation
of electrochemical systems for quite some time. The major
advantage of the method lies within the fact that the frequency
of the signal can be varied over a large range, enabling
resolution of phenomena with different time constants, such
as diffusion and charge transfer. Usually the measurement is
performed with a low-amplitude signal around an equilibrium
state. This makes the method useful for evaluating the
parameters, in a battery electrode, for different state of charge
(SOC) whereas other measurement techniques usually give an
average over a range of SOC.
On Nyquist plots for AC impedance measurements, two
semicircles were observed for all the MH electrodes under
study, i.e., a small semicircle in the high-frequency region and
a large semicircle in the lower frequency region. However, the
interpretations of the AC impedance for MH electrodes have
been controversial up to now. The assignment of the small arc
in the high-frequency region is not very clear at the moment
and is still a matter of controversy. Kuriyama et al. [28]
ascribed the measured high-frequency arc to the contact
resistance between the current collector and the alloy pellet.
Other researchers [29, 30] also assigned the semicircle in the
high of frequency region to the contact resistance between the
current collector and the active material and/or particle-to
particle resistance. Ticianelli et al. [31] assigned the observed
arc in the high-frequency region to the contact resistance
between the current collector and the active material. Züttel
et al. [32] specified that this contact resistance depends on the
chemical states of the contact surface and also on the thickness
of the oxide layer. Yuan and Xu [33] reported that such a
semicircle was also observed for hydrogen storage alloy
ingots, making the assignment to contact resistance
questionable. Khaldi et al. [34] attributed the high-frequency
arc to the behavior of corrosion layer formed on the electrode
J Solid State Electrochem (2014) 18:577–593
surface, but evidence was lacking. However recently, some
researchers [35–39] attributed the features at high frequency
to the charge-transfer reaction.
Several authors [28, 29, 35, 40–46] have modeled different
metal hydride systems. Most of the authors have been using
different equivalent circuits to analyze the mechanism of
hydrogenation/dehydrogenation reactions of the hydride
electrodes, although the impedance diagrams of the metal
hydride electrode are relatively similar. Sometimes, the same
data may be represented by different equivalent circuits. In this
case, it is difficult to find a suitable equivalent circuit.
Mathematical modeling of impedance response has been
performed along two main paths. One approach is to try to
fit impedance data to equivalent circuits, and assign the various
subprocesses to the circuit elements, an approach which has
been taken by many authors [28, 42, 47–49]. Based on an
equivalent circuit model, Kuriyama et al. [28, 47] suggested
that the following parameters need to be taken into account:
hydrogen content, rates of the electrode reactions on alloy
particles, double-layer capacitance, and contact resistance
and capacitance between alloy particles in the electrode. The
limitations of this approach are obviously related to the
difficulties in relating the elements of the equivalent circuit to
the physical processes. The other approach is to develop
physical models describing the processes believed to be
determining for the response. An overview of mathematical
models describing impedance response related to various
processes (chemical/ electrochemical reaction as well as
transport processes) is provided by Lasia [50].
Most of the circuit elements in the model are common
electrical elements such as resistance, capacity, inductance,
constant-phase element, Warburg impedance (semi-infinite
linear diffusion), Warburg impedance (finite-length
diffusion), impedance of porous electrodes, and impedance
for the case of rate control by a homogeneous chemical
reaction. To be useful, the elements in the model should have
a basis in the physical electrochemistry of the system.
Constant-phase elements (CPE) are widely used in
equivalent electrical circuits due to the existence of
commercial software for the fitting of AC impedance
experimental data [51, 52]. The physical meaning of CPE is
still a matter of controversy [53–56]. The CPE behavior is
generally attributed to double-layer capacitance, adsorption,
surface inhomogeneity, roughness, electrode porosity, non-
uniform current and/or potential distributions, etc.
In the literature, different equations for CPE were proposed.
In the following equations, j is the imaginary number
 pffiffiffiffiffiffi
j ¼ −1 and ω is the angular frequency (ω =2πf,f being
the frequency).
Lasia [50] gives the impedance of the CPE as:
Z CPE ¼ 1=T ð jωÞϕ ð1Þ
J Solid State Electrochem (2014) 18:577–593
Where T is a constant in F cm−2sΦ−1 and ∅ is related the
angle to the rotation of a purely capacitive line on the complex
plane plots.
Brug et al. [57] proposed:
Z CPE ¼ Q=ðjωÞ1−α ð2Þ
where Q is a constant (with dimensions Ω cm2 s−(1−α)) and 1−α
has the same meaning as ϕ in Eq. (1).
Zoltowski [53] proposed two definitions, i.e.,
Z CPE ¼ 1=Qa ðjωÞα ð3Þ
and
Z CPE ¼ 1=ðQb jωÞα ð4Þ
The definition according to Eq. (3) was recommended in
ref. [53] because Q a is directly proportional to the active area.
The dimensions of Q a and Q b are Ω−1 m−2 sα or (Ω m2)−1/α
sα , respectively. A combination of these expressions can be
also found. Depending on the formula used, the CPE
parameter is Q, 1/Q , or Q α and, for capacitive dispersions,
the CPE exponent is α or (1−α) with α close to 1 or close
to zero, respectively. The exponent α may acquire different
values that characterize the nature of CPE; at α equal to 0,
0.5, 1, and −1, CPE transforms into the resistance R ,
Warburg impedance W, capacitance C, and inductance L,
respectively [50, 53, 58]. In this case, the CPE becomes an
extremely flexible fitting parameter, but its meaning in terms
of a distribution of time constants is lost. The different
expressions given for the CPE underline that the physical
meaning of this element is not clear. The equivalent circuit
has the character of a model, which more or less precisely
reflects the reality. The equivalent circuit should not involve
too many elements because then the standard errors of the
corresponding parameters become too large, and the model
considered has to be assessed as not determined, i.e., it is
not valid.
In this paper, the thermodynamic and electrochemical
properties of metallic hydrides will be reviewed.
Intermetallic hydride families
The classes of hydrogen storage alloys can be principally or
conventionally classified as AB5-type alloys, AB2-type alloys,
AB3-type alloys, AB-type alloys, Mg-based alloys, and V-
based solid solution alloys. Their performances differ greatly
in terms of specific capacity, activation, rate dischargeability,
and cyclic lifetime. Few archetype materials of these classes
are shown in Table 1. The details of these materials can be
seen in the references given therein. Today, AB5- and AB2-
579
type multicomponent metal hydride alloys are extensively
being studied for their commercial use in Ni-MH batteries.
AB2 compounds
The AB2 hydrogen storage intermetallic compounds have
been investigated extensively because of their potential
application in high-capacity negative electrodes for Ni=MH
batteries. The AB2-type alloys mainly form one of two
structures, either the cubic C15 structure or the hexagonal
C14 structure [70, 71]. The potential AB2 types are obtained
with Mg, Ti, and Zr on the A site. The B elements are
represented mainly by different combinations of 3d atoms,
V, Cr, Mn, and Ni. Previously, we have investigated the
structural and electrochemical properties of C14-based AB2
materials having various combinations of A site elements (Ti
and Zr) [72], and B site elements such as vanadium [73], tin
[74], manganese [75], aluminum [76], chromium [77, 78],
nickel [77], and iron [79]. Co-substitution has also been
investigated extensively in AB2 alloys as a path to improving
performance for both hydrogen storage and battery
applications [80–84]. The earliest studies were done by
Shaltiel et al. on Zr(Cox M1−x )2 (M = V, Cr, Mn) alloys, which
found that as the Co-content increased, the PCT plateau
pressure increased, and the absolute value of heat of formation
(|ΔH |) decreased [80]. Honda et al. substituted Co for Mn in
C14 Zr(Mn1−x Cox )Alz and found that as the cobalt content
increased the plateau pressure/hydrogen absorption speed
increased but the storage capacity decreased [81]. Given their
excellent hydrogen absorption ability and ease of activation,
Zr-based intermetallic compounds with C14/C15-laves
structure have potential application in the fields of hydrogen
storage and separation and have been the subject of many
studies over the past few decades. The hydrogen absorption
capacity of ZrV2 can be as high as 4.8 H/M at 1 atm hydrogen
partial pressure without any change in crystal structure [85].
However, ZrV2 hydrides are too stable to release hydrogen
easily which makes it for ZrV 2 difficult to meet the
requirements of rechargeable batteries and applications in
the nuclear industry [85]. In addition, the high cost of
vanadium and high pyrophoricity of ZrV2 are also obstacles
for practical applications. Hyper-stoichiometric AB2 alloys
are advocated for the higher Ni-content resulting in better
high-rate dischargeability [86–88], higher hydrogen plateau
pressure which contributes to a higher reversible capacity [86,
89], an easier activation [83, 90], an increased amount of C15
phase for a higher capacity [89, 91, 92], a reduction of non-
storage secondary phases such as Zr7Ni10 and Zr9Ni11 [91,
92], creation of BCC phase with higher storage capability
[93], and an increase in cycle stability [94]. The Laves phase
series of compounds has attracted large attention in the last
decade due to their good hydrogen storage capacity. However,
AB2-type alloys suffer from poor activation.
580 J Solid State Electrochem (2014) 18:577–593

Table 1 Classification of intermetallic system for hydrogen storage

Properties AB5 A2B AB AB2 AB3

Specific example LaNi5 Mg2Ni TiFe TiMn2 LaNi3

Structure Hexagonal Cubic Cubic Hexagonal or cubic Rhombohedral
Hydrides LaNi5H6 Mg2NiH4 TiFeH2 TiMn2H2 LaNi3H5
Temperature Room temp ~300 °C Near room temp Near room temp Near room temp
Storage capacity (wt%) 1.43 3.8 1.75 1.7 1.2
References [59–61] [62–64] [65, 66] [67, 68] [69]

AB5 compounds
Among the various types of hydrogen storage alloys, the
AB5-type alloys were the first generation to be used as
electrode materials. The AB5-based compounds have a
hexagonal or orthorhombic structure with the CaCu5-type
lattice [95]. In the beginning, the LaNi5 parent compound of
AB5-type alloys was systematically investigated as an active
negative electrode material for Ni-MH batteries [4]. The
discharge capacity of LaNi5 alloy, however, decreased rapidly
with the increase of the charge/discharge cycles because the
alloy pulverized and oxidizing La into La(OH)3 in the alkali
solution on cycling [4]. The surface layer of the LaNi5 alloy is
formed of Ni and La2O3. The oxidation layer has a thickness
of about 40 to 50 nm (see Fig. 1. [96]). Willems and
coworkers [4, 5] have discovered that the partial substitution
of Ni by Co was an effective way to enhance the charge/
discharge life cycle of LaNi5 alloy due to the decrease of the
volume expansion and hence pulverization during the
charge–discharge cycling. Since then, the electrochemical
properties of the RENi5-based hydride electrode alloys have
been investigated extensively for the further improvement of
the overall properties and the reduction in price of this type of
alloy. The most popular ways are the multialloying, namely
the partial substitution of Ni (B side) by Co, Mn, Cr, Fe, Zr,
Al, Ti, Ca, Cu, and Si, and the replacement of La (A side) by a
Mischmetal (cerium-rich mischmetal Mm or lanthanum-rich
mischmetal ML) [7, 97–101]. Capacities for various substituted
compounds are given in Table 2 [102]. In all cases, the
pseudobinary compounds show smaller capacity than the
corresponding parent compound.
The AB5-type hydrogen storage alloy Mm (Ni, Mn, Co,
Al)5 is one of an alloy series which are being extensively used
now. The alloy of composition MmNi3.55Mn0.4Al0.3Co0.75
was shown to meet the minimum requirements for a practical
battery with respect to cost, cycle life, and storage capacity
[103, 104]. Cobalt, a key element to keep long cycling life,
is the most expensive element in the commercial hydrogen
storage alloys and 10 wt% Co constitutes about 40–50 %
of the total cost of the raw materials [105–115]. Therefore,
it is interesting to investigate low-Co and/or Co-free AB5-
type alloys.
Many works have demonstrated the possibility and
application of the partial replacement of Cu, Zn, Mn, Al, Fe,
Si, Cr, Sn, etc. for Co. Copper was used to substitute Co in the
alloys MlNi3.5Co0.7−7x Cu8x Al0.8−x (x =0–0.1) [116, 117] and
it is found that the electrochemical properties of the alloys is
not affected when 50 % of Co content was substituted by Cu
and the cycle life for the alloys would decrease with the
increase of Cu content. Ma et al. [118] researched the
electrochemical properties of the Co-free MlNi 4.45 −
x Mn0.4Al0.15Snx alloys and found that the cycle life of the
alloy x =0.4 is the best for those of all the alloys; however, its
discharge capacity is only 269.1 mAh g−1. Cr, Cu, and Si of
three elements were used to substitute Co in a united way in
the alloy system of MmNi3.65Co0.22Mn0.36Cr0.2Cu0.2Si0.1 by

Fig. 1 Representation of the

surface of LaNi5. The surface
layer is formed of Ni
and La2O3 [96] 40-50 nm

La2O3 Ni LaNi5
J Solid State Electrochem (2014) 18:577–593
Table 2 Hydrogen capacity for various pseudo-binary AB5-type alloys
at the pressure indicated between brackets
Composition Csg (H/f.u.), (PH2 (bar)) Cel (mAh g−1)
LaNi5 6.24 (25) 387
LaNi4.7Al0.3 5.85 (10) 370
LaNi4.25Co0.75 6.23 (10) 386
LaNi4Cu 5.45 (10) 334
LaNi4Fe 5.45 (10) 327
LaNi4.5Sn0.5 5.25 (10) 304
LaNi4Mn 5.82 (10) 364
LaNi3.55Mn0.4Al0.3Co0.75 5.60 (10) 334
MnNi3.55Mn0.4Al0.3Co0.75 5.30 (10) 332
Hu [106] and it was found that the capacity decay was 25.6 %
after 300 full cycles. But the discharge capacity of the alloy
above was only 273 mAh g−1. Recently, it is reported that the
electrochemical performances were improved through the
additive of some active elements. Tang et al. [119] developed
a low-cobalt alloy through addition of Mg, the discharge
capacity of the alloy was 320 mAh g−1 and the capacity decay
was 12 % after 300 charging/discharging cycles. Wei et al.
[120] found that through the addition of trace of Ca element,
the cycle life of the low-cobalt alloys can be improved. Zhang
et al. [121] found that when a trace of B element was added in
the low-Co AB5-type alloy, the cycle life of the as-cast and
quenched alloys could be enhanced dramatically.
Iron is one of the relevant candidates for cobalt substitution
in AB5 MH alloys due to its atomic radius, number of
electrons, and electronegativity being similar to those of Ni
and Co. Zuttel et al. [122] replaced a part of the cobalt by iron
in the LmNi3.8Al0.4Mn0.3Co0.3Fe0.2 compound. They found a
long electrochemical cycle life. At 40 °C, there is a loss of
only 0.15 % of the capacity after 200 cycles. Hasegawa et al.
[123] found that iron has a beneficial effect on cyclic stability.
Cocciantelli et al. [124] also found a beneficial effect of Fe
substitution in MmNi3.8−x Mn0.33Al0.4Co0.51Fex (x =0, 0.16)
compounds and scanning electron microscopy observations
showed that the addition of iron reduced their decrepitation. It
has been shown that alloys in which cobalt is partially
substituted by iron, which is relatively inexpensive, maintain
a good cycling stability [22, 125–135].
AB3 compounds
However, none of the available electrode alloys including
AB5 and AB2 types can meet the specification of the power
battery because of the limitation of their properties, such as the
low discharge capacity of the AB5-type electrode alloy and the
poor activation capability of the AB2-type Laves phase
electrode alloy. Therefore, the research in this area has been
focused on finding new type electrode alloys with higher
581
capacity and longer cycle life. Recently, some of the new
series of R-Mg-Nin ( R = rare earth, 2<n <4) alloys mainly
contain PuNi 3 -type (AB 5 + 2AB 2 = 3AB 3 ), Ce 2 Ni 7 -type
(AB5 +AB2 =A2B7) or Pr5Co19-type (3 AB5 +2AB2 =A5B19)
were considered to be the most promising candidates owing to
their higher discharge capacities (360–410 mAh g−1) and low
production costs. This series of compounds have the generic
formula ABx with x =(5n +4)/(n +2). Kadir et al. [136–139]
revealed that this kind of alloys hold PuNi3-type
rhombohedral structure. Now, the main problem for this series
of alloys to be used for industrialization is the poor cyclic
stability.
In order to improve the cyclic stability of La-Mg-Ni-type
hydrogen storage alloy electrodes, the partial substitution of
Ni with many transition metals such as Co, Mn, Fe, Cu, Al,
zinc, etc. [140–142] and the partial substitution of La with Ce,
Pr, and Nd [143–145] have been carried out extensively.
However, their poor cyclic stability hinders the practical
applications of these alloys. Recently, many efforts have been
made to improve the cyclic stability of AB3-type La-Mg-
based hydrogen-storage alloys. Investigations have shown
that both the cyclic stability and electrochemical
characteristics of these alloys can be significantly improved
by partial substitution of Al, Cu, Mn, Co, and other elements.
Among these elements, Co is thought to be important for
attaining a satisfactory cycling lifetime of an La-Mg-based
alloy, and it seems to be indispensable in these alloys.
According to recent studies, the discharge capacity of La-
Mg-Ni AB3-type alloys with Co element could reach 380–
400 mAh g−1 [142, 146–150]. The element Co could be added
into AB3-type alloys to guarantee the cycling stability and
high discharge capacity when it works in AB5-type alloys
[151]. Considering that Co element is not environmentally
friendly enough and can increase the cost of batteries, there are
some work done on low-Co alloys in which Co was
substituted by Fe or other elements [152, 153]. Co-free
hydrogen storage alloy got attention and there are some
studies on it in recent years [154–157].
AB compounds
The AB-type alloys are promising materials for hydrogen
absorption/desorption from the gas phase as well as for
reversible electrochemical charging/discharging (metal
hydride electrodes) [158–162]. The main representative of
this class of materials is the intermetallic compound TiFe,
which crystallizes in the cubic CsCl-type structure and can
absorb reversibly up to 1.9 wt% hydrogen. The application of
TiFe has been limited due to the poor absorption/desorption
kinetics in addition to the complicated activation procedure
and high equilibrium pressure for the hydride formation at
room temperature [65]. Several studies were carried out to
understand the reasons of such difficult activation. A
582
summary of the results was published by Schlapbach and
Riesterer [163]. During activation, the TiFe lattice expands
and contracts about 20 % of its volume. Hydrogenation of
TiFe by solid–gas reaction can only be achieved after severe
activation treatments due to its high sensitivity to surface
poisoning by gaseous impurities [164, 165]. However, partial
substitutions of Fe by Mn and Ni are successful for improving
the hydrogenation reactivity of the alloy and permit the
adaptation of its plateau pressures at will for applications on
hydrogen storage [166]. In recent years, more AB-type
hydrogen storage alloys consisting of Ti, Zr, or Hf on the A
side and Fe, Ni, Al, Co, Mn, or Sn on the B side have been
investigated [167–171]. Szajek et al. [172] reported that the
respective replacement of Fe in TiFe by Ni and by Mn
improved not only the discharge capacity but also the cycle
life of the electrodes prepared from nanocrystalline TiFe
alloys, synthesized by mechanical alloying and annealing.
TiFe 0.25 Ni 0.75 showed a high discharge capacity of
155 mAh g−1 on the third cycle [169]. Cuevas et al. [173]
have shown that martensitic Ti0.64Zr0.36Ni exhibited much
higher reversible capacity, about 330 mAh g−1. Nevertheless,
the electrochemical properties of this system of alloys are
unsatisfactory [174].
Although the Ti-Ni system has been studied for many
years, it is still in an active research topic [174–176].
Thermodynamic properties of hydrides
Half-cell reactions at positive and negative electrodes in
nickel-metal hydride batteries and the overall reaction are
represented in the following equations (Fig. 2).
Positive : NiðOHÞ2 þ OH− ⇄NiOOH þ H2 O þ e− ð5Þ
Negative : M þ H2 O þ e− ⇄MH þ OH− ð6Þ
Overall : NiðOHÞ2 þ M⇄NiOOH þ MH ð7Þ
Here, M represents the hydrogen storage alloy, and MH
refers to the alloy in the hydride form. During charging the
positive electrode, nickel hydroxide (Ni(OH)2) is oxidized to
nickel oxyhydroxide (NiOOH) (Eq. 5) while at the negative
electrode, metal hydride (MH) is formed by water electrolysis
(Eq. 6). As a result, the overall reaction is represented by a
transfer of hydrogen between M and Ni (OH)2 (Eq. 7).
The charging process at the negative electrode is
represented by the following equations in more detail:
H2 O þ e− ⇄Had;s þ OH− ðcharge transferÞ ð8Þ
2Had;s ⇄H2 ðhydrogen evolutionÞ ð9Þ
Had;s þ H2 O þ e− ⇄H2 þ OH− ðhydrogen evolutionÞ ð10Þ
J Solid State Electrochem (2014) 18:577–593
Had;s ⇄Hab;s ðhydrogen absorptionÞ ð11Þ
Hab;s ⇄Hab;b ðhydrogen diffusionÞ ð12Þ
where Had,s, Hab,s, and Hab,b represent adsorbed hydrogen on
the alloy surface, absorbed hydrogen near the alloy surface,
and absorbed hydrogen in the bulk alloy, respectively.
First, Had,s is produced on the alloy surface by a charge
transfer reaction (Eq. 8) known as the Volmer reaction. Then,
the atomic hydrogen is absorbed into the alloy (Eq. 11) in
addition to hydrogen evolution due to a coupling of the atomic
hydrogen, known as the Tafel reaction (Eq. 9), or an additional
charge transfer of the atomic hydrogen known as the
Heyrovsky reaction (Eq. 10). Equations 9 and 10 are side
reactions in the charging process. The absorbed hydrogen
diffuses from the surface to the bulk (Eq. 12) before hydride
formation.
Hydrogen absorption induces a large expansion of the unit
cell volume of the metallic compounds. This volume increase
is closely related to the capacity and ranges between 2 and
3 Å3 per H atom [177]. The discrete volume expansion ΔV/V
observed between the two phases α and β on the equilibrium
plateau can vary from 8 to 30 %. Hydrogen absorption in
intermetallic compounds is characterized by a mean hydrogen
capacity of about 1.1 H/M (hydrogen atom per metal atom).
However, this value can vary in very large proportions
depending on the compounds and the largest reported value
reaches 4.5 H/M for BaReH9 [178]. The stability of the
formed hydride is determined by its hydrogen equilibrium
pressure at a given temperature. In general, for
electrochemical applications the most suitable hydrogen
desorption plateau pressure of a metal hydride should be
between 0.1 and 1 atm at room temperature [179].
Metal hydrides for battery applications are characterized in
terms of their hydrogen storage capacity at moderate hydride
stability and approximately constant equilibrium pressure
during hydride phase transformation. Data on these properties
can be obtained from pressure–composition–temperature
(PCT) isotherms, which describe the dependence of the
hydrogen equilibrium pressure on the amount of hydrogen
absorbed or incorporated into the hydrogen storage material at
various temperatures. The PCT isotherms can also be used to
identify different phases in metal hydride alloys. Hydrogen
concentration at various stages such as in the α phase, during
transition of α phase to β phase, and in the β phase in
equilibrium with the α phase can also be obtained from
PCT isotherms [180]. Thermodynamic properties such as the
change in enthalpy (ΔH) and the change in entropy (ΔS) of
hydride formation can be derived from the temperature
dependence of the adsorption–desorption isotherms by using
the Van't Hoff equation [181]:
 
ln PH2 =P ¼ ΔH=RT−ΔS=R; ð13Þ
J Solid State Electrochem (2014) 18:577–593
Fig. 2 Schematic representation
of the concept of a sealed
of rechargeable
Ni/MH battery
where P H2 is the equilibrium hydrogen pressure upon α to β
hydride phase conversion, determined from the mid-plateau
values of the PCT isotherms, P ° is the standard pressure, R is
the gas constant, and T is the temperature. The enthalpy and
the entropy of hydride formation/decomposition are derived
from the slope and intersect of the accordingly obtained linear
dependence of the pressure logarithm plotted as a function of
the reciprocal value of the temperature (van't Hoff plots). The
Gibbs free energy of formation (ΔG ) was calculated
according to:
ΔG ¼ ΔH−T ΔS; ð14Þ
Thus, the hydrogen pressure can be optimally adjusted by
changing the composition and the types of alloying elements.
Experimental tests are, however, necessary to prove the
validity of these theoretical predictions.
The enthalpy of hydride formation is an important
parameter that serves for assessment of the alloy applicability
as hydrogen absorber in various applications. Kleperis et al.
[161] have stated that if the value of ΔH ranges between −25
583
and −50 kJ mol−1, the alloy is a viable candidate for battery
applications. Hong [182] has come up with a little lower values
for the heat of alloy hydride formation that are
encompassed in the range −15 and −40 kJ mol−1. A value
lower than −15 kJ mol−1 renders the alloy not sufficiently
stable for charging at room temperature, whereas a ΔH
value exceeding −50 kJ mol−1 should render it too stable
for room temperature discharge. In practice, ΔH is an index
of the thermochemical stability of metal hydride electrodes.
A high ΔH value would signify a high degree of stability
of the hydride and low dissociation pressures, which means
that a high temperature is required to decompose the alloy
to release the hydrogen.
On the contrary, an alloy with a low ΔH value would have
characteristics opposite to those discussed above [183].
Though many investigators estimated the reaction enthalpies
of various metal hydride alloys during absorption and
desorption of hydrogen [184–193], no one has precisely
reported the effect of hydrogen concentration on the reaction
enthalpies of the metal hydrides. In general, the difference in
the standard entropy between a metal hydride alloy and its
584
hydride compound is virtually negligible and normally does
not exceed 10 J mol−1 K−1. The entropy change with hydride
formation is mainly due to a standard entropy loss of the
hydrogen gas (−130.858 J mol−1 K−1at 298 K). This suggests
that (as a first approximation) ΔS could be considered as
invariable and in turn independent upon the nature of the
metal hydride alloy [194].
PCT diagrams can be constructed for metal hydride alloys in
two ways, namely a gas–solid PCT isotherm and an
electrochemical PCT isotherm. The PCT isotherms can also be
used to identify different phases in metal hydride alloys.
Hydrogen concentration at various stages such as in the
α-phase, during transition of α-phase to β-phase, and in the
β-phase in equilibrium with the α-phase, can also be obtained
from PCT isotherms [195]. A representative picture of PCT
isotherm for an ideal hydride-forming material and van't Hoff
diagram are shown in Fig. 3 [196]. Three domains can be
observed. At low H content (x <α max in H/M), a solid solution
single phase domain occurs, the so-called a -phase, where
hydrogen absorption/desorption can be described by the reaction:
dx
MHx þ H2 ⇄MHxþdx ð15Þ
2
For α max <x <β min, there is a two-phase domain, where the
saturated α-phase, with composition x =α max, transforms into
the β-phase, with composition x =β min. It corresponds to the
plateau pressure that extends in composition as long as the
following equilibrium reaction takes place:
y−x
MHx ðαmax Þ þ H2 ⇄MHy ðβ min Þ ð16Þ
2 calculated from EC isotherms during charge and discharge are
Fig. 3 Typical PCI curves for
hydrogen absorption–desorption
in intermetallic compounds.
Inset, van't Hoff plot
(from ref. [196])
J Solid State Electrochem (2014) 18:577–593
The formation and decomposition of the hydride occur on
the plateau and is usually characterized by a hysteresis
phenomenon. The hydrogen equilibrium pressure during
absorption is higher than that of desorption. This is commonly
attributed to the extra energy necessary to overcome the
constraints related to the lattice expansion.
For x >β min , again a solid solution single-phase domain
occurs, corresponding to the β -phase, which can be also
described according to Eq. 15.
The charge–discharge curves under galvanostatic
conditions are electrochemical equivalents of the PCT
isotherms of the gas–solid phase reaction. In fact, there is a
thermodynamic correlation between the equilibrium pressure
measured in the gas phase reaction and the electrode potential
measured in an electrochemical cell. The equilibrium potential
of the MH electrode is related to the hydrogen equilibrium
pressure by the Nernst equation [197]:
RT
E eq ¼ E0 − lnðPH2 Þ ¼ −0:9324−0:0291 lnðPH2 Þ ð17Þ
2F
where E 0 =−0.9324 V vs. Hg/HgO, R is the gas constant (in
joule per Kelvin per mole), T is the temperature (in Kelvin),
and F is the Faraday constant (in coulomb per mole). The
electrochemical (EC) isotherms differ slightly from the gas-
phase isotherms during absorption in that the inflection in the
pressure at the end of absorption is absent, possibly because
internal pressures are limited to 1 atm in the basic cell. The
discharge isotherms, on the other hand, bear a greater
resemblance to the gas-phase isotherms. The plateau pressures
J Solid State Electrochem (2014) 18:577–593 585

generally comparable to those measured by gas-phase
isotherms. The electrochemical approach to construct PCT
isotherms, therefore, is a simple and convenient alternative
procedure. Despite the importance of the heat of hydride
formation of metal hydrides for battery applications, sufficient
studies have not appeared in the literature, especially by
electrochemical methods.
A schematic P–C isotherm hysteresis of metal hydride
alloy is shown in Fig. 4. The PCT isotherm absorption–
desorption hysteresis is calculated by the equation [198]:
hysteresis ¼ lnðPa =Pd Þ ð18Þ
where P a and P d are the absorption and desorption
equilibrium pressures at 50 % of the reversible storage. The
hysteresis in metal hydrogen systems has been attributed by
many authors to the formation of defects related to plastic
deformation during both hydride formation and
decomposition [199, 200]. This has been demonstrated for
LaNi5 by Kisi et al. [201], though in that work planar defects
were invoked instead of dislocations which were later
demonstrated to be the dominant lattice defects [202]. During
the α - to β -phase transition with the hydrogenation and
dehydrogenation of the alloy electrode, the lattice parameters
are enlarged and shrunk suddenly rather than slowly and
continuously, which leads to the formation of defect structures
and introduces a large amount of cracks in the bulk of the alloy
particles. These constraints are partially relaxed during
desorption. For the majority of the AB5- and AB-type
intermetallic compounds, the hysteresis decreases between
the first and second cycle of absorption [200], which is due
to a decrease in the absorption pressure plateau while the
desorption pressure remains unchanged. Adzicet al. [203]
reported that the lack of hysteresis near room temperature in
multicomponent AB5 hydrides is not unusual, but it is almost
P (bar)
always present in the less complex binary and ternary systems
(see Fig. 5).
For AB3-type alloys, Peng and Zhu [204] have investigated
the microstructure and hydrogen absorption/desorption
properties of Ml0.7 Mg0.3Ni3.2 alloys and they found that the
absorption curve of the first absorption/desorption cycle is
different to that of the following cycles that are nearly the
same. The desorption curves of the first cycle and the
following cycles are nearly the same (see Fig. 6 [204]). After
the first absorption/desorption cycle, a lot of defects and
cracks are formed, which relax the stress resulted from
hydrogenation process [200]. Therefore, the absorption
plateaus pressure decrease in subsequent cycles.
For the multi-phase AB2 MH alloys, the PCT isotherms can
be considered as the composites of many hydrogen storage
sites with various metal hydrogen bond strengths, which are
different from AB5 MH alloys with simpler phase components
[205]. PCT hysteresis in AB2 alloys has been demonstrated to
be closely related to the unit cell aspect ratio (a/c) of the major
C14 phase [78], pulverization rate during gaseous phase
cycling [206], and average electron density [33]. The
absorption–desorption characteristics of MmNi5−x Al(Mn)y –
z Mz and MmNi5−x Al(Mn)y Mz (M = Co, Cr, Cu, Nb, Ti, V, Zr;
x =0.3–0.5; y =0.3–0.5; z =0.05–0.1) have revealed that the
substitution or addition of element M reduces the hysteresis
[207]. The hysteresis for MmNi4.7Al0.3 M0.1 decreased for
substitution of M in the order of: Zr > Co > Cr > Ti, V >
Cu. In MmNi5−x Mx (M = Mn, Al, and Sn; x =0.4 and 0.8), the
partial substitution of Ni with Al, Mn, and Sn in MmNi5
resulted in the lowering of hysteresis loss upon hydrogenation
[208]. Gamo et al. [209, 210] investigated the Ti–Mn alloys in
detail. They showed that TiMn2-based pseudo-binary alloys,
such as Ti0.9Zr0.1Mn1.4Cr0.4 V0.2, exhibit good properties for
hydrogen storage. However, the hysteresis of this alloy is still
large and the hydrogen absorption pressure is as high as ≈
20 atm. Hagstrom and his coworkers measured the PCT

absorption

Hystérésis
H2

désorption

α max β min
X (H/mole)
Fig. 4 Generalized illustration of pressure-composition hysteresis in
metal–hydrogen systems Fig. 5 PCI isotherms for LaNi5 and MmNi3.55 Co0.75Mn0.4 Al0.3 (ref. [203])
586
Fig. 6 PCI isotherms of the as cast Ml0.7 Mg0.3Ni3.2 alloy measured at the
first and second hydrogen absorption/desorption cycles (ref. [204])
characteristics of some Ti-based AB2 and CeLaNi-based AB5
materials and found that substitutions of V and Co
considerably reduce the hysteresis effect [185].
Electrochemical kinetics of metal hydrides
Generally, the electrochemical kinetics of hydrogen storage
alloy electrodes is mainly determined by both charge-transfer
process on the alloy surface and hydrogen atom diffusion
within the bulk of the alloy. The former can be characterized
by charge-transfer resistance (R ct) or the surface exchange
current (I 0), while the latter can be determined by hydrogen
diffusion coefficient. The exchange current density reflects a
charge transfer capability in an electronic transformation from
adsorbed hydrogen to hydrogen ion at the discharge process
and from hydrogen ion to adsorbed hydrogen at charge
process. The increase in the exchange current density leads
to an improvement in the high-rate discharge capability.
Previous efforts have investigated the dependence of the
exchange current density upon hydrogen content in the alloy.
Using linear polarization (LP), Tafel polarization, and
electrochemical impedance spectroscopy techniques, Popović
et al. [211] found that the exchange current density of the
LaNi4.15Co0.43Mn0.40Fe0.02 alloy electrode increases with
increasing hydrogen concentration in the alloy electrode and
the values of the exchange current determined by AC
impedance are in good agreement with values obtained by
micropolarization and Tafel polarization (see Fig. 7).
Ratnakumar et al. [23] and Witham et al. [212] found that
exchange current densities estimated from linear polarization
for LaNi5−x Gex and LaNi5−x Snx alloys were in agreement
with those from AC impedance, but were quite different from
the values obtained from Tafel polarization. Wang et al. [213]
proposed that this discrepancy may be caused by a neglect of
the effect of hydrogen transfer between the absorbed and
J Solid State Electrochem (2014) 18:577–593
Fig. 7 Variation of the exchange current with state of charge determined
by DC anodic (filled triangle) and cathodic (filled square)
micropolarization measurements, AC impedance (empty square) and
the anodic Tafel polarization measurements (filled circle) (ref. [211])
adsorbed states. Conventional Tafel polarization method
cannot be applied to estimate the exchange current density for
porous metal hydride system due to presence of internal mass
transfer effects and internal ohmic voltage drop of the electrode
[214]. Ramya et al. [38] have studied the effect of nickel
substitution on the electrochemical properties of TiMn2−x Nix
alloys and determined the exchange current density of the
alloys using AC impedance. They found that the exchange
current density of the TiMn2 − x Nix alloys increases with
increasing SOC. Popov et al. [215] determined the exchange
current density of La0.65Ce0.35Ni3.55Co0.75Mn0.4A10.3 alloy
electrode from linear polarization at different states of charge.
They reported that the exchange current density increases with
decreasing the hydrogen content in the alloy and reaches a
maximum value at approximately 15 % of SOC. Then, the
exchange current density starts to decrease with decreasing the
hydrogen content in the α phase region of the alloy. Using AC
impedance impedance, Muruganantham et al. [39] found that
the exchange current density of the MnFe2 alloy electrode
increases significantly on charging the electrode: this indicates
that the electrocatalytic activity on the surface of the alloy is
greatly improved which, thereby, reduces the overpotential
during the charge–discharge process. The exchange current
density of the electrode varies from 18.5 mA g−1 at 16.66 %
SOC to 25.5 mA g−1 at 100 % SOC.
In our previous studies [216, 217], we have shown a similar
dependence of the exchange current density upon hydrogen
content in the LaNi3.55Mn0.4Al0.3Co0.4Fe0.35 metal hydride
alloy electrode using linear polarization and AC impedance.
When the SOC of the electrode is less than about 50 %, the
exchange current density increases rapidly with hydrogen
content and then remains almost constant; however, as the
J Solid State Electrochem (2014) 18:577–593 587

hydrogen content increases the exchange current density also differences in the results can be attributed to differences in
increases due to the changes from the α to the β phases and composition and in real surface area. The kinetics of the
also due to variations in the alloy electroactive area. Recently charge transfer reaction is hardly influenced by the
[216], in our work, we have demonstrated that the values of composition of the bulk electrode material. The
the real surface area increases from 3.74 to 4.2 cm2 with the electrocatalytic activity, which is reflected by the exchange
increase in SOC of the metal hydride electrode from 0 to current density, is mainly determined by the chemical
100 %. Comparing the values of I 0 calculated from LP and composition and the surface properties of the electrode such
AC impedance measurement, it can be found that the values of as oxide thickness, electrical conductivity, surface porosity
I 0 estimated from AC impedance are slightly higher than the and topology, surface area, and degree of catalytic activity.
values obtained from LP. The difference in the values of I 0 The hydrogen diffusion in a charge–discharge reaction is
may be due to the magnitudes of the polarization resistance R p influenced by both the micro- and the macro-structure of the
and the charge transfer resistance R tc estimated from LP and alloy. The diffusion coefficient of atomic hydrogen in the solid
AC impedance, respectively. In generally, the polarization phase was shown to depend on the strength of the metal–
resistance is composed of ohmic resistance, charge transfer hydrogen interaction and the hydrogen concentration in the
resistance, and diffusion resistance. Zheng et al. [49] found bulk since this is a characteristic of mass transport in metal
that, for LaNi4.25Al0.75, the resistance measured from linear hydride electrodes [24]. The hydrogen diffusion coefficient,
micropolarization is approximately equal to the sum: the D H, is one of the most important kinetic parameters for MH
charge-transfer, hydrogen-transfer, and hydrogen-diffusion alloy because the hydrogen diffusion process limits the rate of
resistances, all three measurable from AC impedance battery reactions in many cases. Till now, there have been a
spectroscopy. Similarly, Wang et al. [213] found that the large number of reports for determining the diffusion
resistance measured from the linear micropolarization gives coefficient of hydrogen in various metal hydride electrodes
the total resistance of the hydriding–dehydriding reactions, using various electrochemical techniques, including current-
and it reduces to the exchange current only when the step method [24], potential-step method [220], cyclic
electrochemical reaction is rate determining. The resistance voltammetry [221], electrochemical impedance spectroscopy
measured from linear micro polarization is approximately [222], and galvanostatic intermittent titration technique [223].
equal to the sum of three resistances measured from AC The potential-step method, a simple and convenient
impedance, namely charge-transfer, hydrogen transfer, and technology, is widely used to study the hydrogen diffusion
hydrogen-diffusion resistances; however, when the SOD is coefficient.
high, the resistance measured from linear micro polarization is In our recent studies [216, 224], the constant-potential
higher than total resistances measured from AC impedance discharge and AC impedance measurements are used to
[213]. The values of exchange current density I 0 for a number evaluate the diffusion coefficient of hydrogen in the
of alloys, found in the literature, are compiled in Table 3. The LaNi3.55Mn0.4Al0.3Co0.4Fe0.35 metal hydride electrode at
various SOC. We have shown that the diffusion coefficient
increases with the increase of hydrogen concentration in the
Table 3 Values of exchange current density for a number of hydrogen
storage alloys
alloy (see Figs. 8 and 9). The value of D H estimated from
constant-potential discharge in is around 2.99×10−11 cm2 s−1
Alloys SOC (%) I 0 (mA g−1) Method References at 60 % SOC [224] and then obtained from AC impedance is
LaNi3.55Mn0.4Al0.3Co0.4Fe0.35 0 211.60 EIS our work [216]
around 1.34×10−11 cm2 s−1 at the same SOC [216]. A similar
40 307.00 concentration dependence where the diffusion coefficient
100 322.18 increases with hydrogen concentration has been seen
12 33.50 LP our work [217] previously [211, 225–227]. The transport of hydrogen in
50 54.52 MH takes place by a hopping mechanism involving two types
100 53.60
of hydrogen motion [228, 229]. Hydriding of the metal begins
MmNi3.6Co0.8Mn0.4Al0.2 0 29.10 EIS [33]
50 21.12
with a rapid diffusion of a small amount of H into the interior
0 26.84 LP
of the alloy to produce a dilute solid solution denoted as the α
50 20.03 phase [230]. As the hydrogen dissolution proceeds, the α
MmFe2 16.66 18.5 EIS [39] phase is gradually supersaturated with hydrogen in its surface
50 18 region and the β hydride starts to deposit [231]. At the end of
100 25.5
the charging, the entire α solid solution is converted and the
Zr0.5Ti0.5 V0 .5Ni1.3Cr0.2 100 104 LP [218]
alloy particle has hydride in the β phase [232].
PrNi3 50 208.71 LP [219]
LaNi3 50 209.46 Wicke and Brodovsky [233] reported that the apparent
YaNi3 50 215.27 diffusion coefficient is dependent on the hydrogen content in
the alloy. It may also be mentioned that for microcrystalline
588
1.6
1.4
cm s )
2 -1
1.2
-11
D (*10
H
0.8
0.6
0 20 40 60 80 100
SOC (100%)
Fig. 8 Variation of the hydrogen diffusion coefficient of the
LaNi3.55Mn0.4Al0.3Co0.4Fe0.35 alloy with state of charge determined by
AC impedance measurements (our work [216])
LaNi3.94Si0.54 films and also for LaNi4.15Co0.43Mn0.40Fe0.02,
the diffusivity was reported to increase with increasing
hydrogen concentration (expanded lattice) in the alloy [211,
225]. Using the galvanostatic intermittent titration technique
(GITT), Yang et al. [226] found that the diffusion coefficient
increases substantially as the SOC increases. The average value
of that the diffusion coefficient is around 2.2×10−11 cm2 s−1
above 20 % SOC. Ciureanu et al. [227] made electrochemical
studies on Ni64 Zr36 and determined the diffusion coefficient of
hydrogen using the chronopotentiometric method. They found
a strong dependence of the diffusion coefficient on the
hydrogen concentration. The values increased from 2.2×
10−10 to 4.5×10−10 cm2 s−1 for H/M ratios of 2.65 to 6.36,
respectively. Using AC impedance, Haran et al. [27] found that
the diffusion coefficient of hydrogen in LaNi4.27S0.24 increases
with increasing SOC. The diffusion coefficient varies from
1.671×10−10 cm2 s−1 at 45 % SOC to 3.851×10−11 cm2 s−1
at 0 % SOC.
However, some authors show results to the contrary. Using
constant potential discharge (CPD), constant current discharge
(CCD), galvanostatic intermittent titration (GIT), cyclic
voltammetry (CV) and AC impedance techniques, Yang
Fig. 9 Variation of the hydrogen diffusion coefficient of the
LaNi3.55Mn0.4Al0.3Co0.4Fe0.35 alloy with different state of charge
determined by constant-potential discharge technique (our work [224])
J Solid State Electrochem (2014) 18:577–593
et al. [221, 223, 234] reported that the hydrogen diffusion
coefficient of the MlNi3.75Co0.65Mn0.4Al0.2 alloy electrode
increases with the increase of depth of discharge. The value
of hydrogen coefficient diffusion determined by CPDT,
CCDT, GITT, and AC impedance differ. Using potential step
method, Iwakura et al. [220] found that the hydrogen diffusion
coefficient of the MmNi4.2Al0.5 M0.3 (M = Cr, Mn, Fe, Co, Ni)
alloy decreased with the increase of hydrogen concentration in
it. Using potential intermittent titration and potentiostatic
methods, Feng et al. [235, 236] reported that the hydrogen
diffusion coefficient in a LaNi4.7Al0.3 metal hydride electrode
increases with the increase of depth of discharge. The same
dependence of the diffusion coefficient upon hydrogen
cotenant was also reported by Kum et al. [237] using
potential-step technique.
Despite this diversity, there is a point upon which various
authors agree; the existing decrease of the hydrogen diffusion
coefficient, during the discharge of the MH electrode, with an
increasing concentration of hydrogen initially absorbed into
the alloy electrode [24, 220–223, 235–238]. This
phenomenon is attributed to the existence of hydrogen–
hydrogen and/or hydrogen–constitutive intermetallic host
interactions [220, 237].
The values of the diffusion coefficient of hydrogen D H for a
number of alloys, found in the literature, are compiled in
Table 4. However, the values of the hydrogen diffusion
coefficient in rare-earth systems vary over 8 orders of
magnitude at room temperature (from 10−6 to 10−14 cm2 s−1).
These widely varying values of D H may be due to differences
in the microstructure, metal stoichiometry and composition of
the alloys, differences in experimental methods, and also
differences in the hydrogen concentrations in the various
alloys. The microstructure of the alloys depends on their
preparation and hydrogenation. The hydrogen diffusion
coefficient can also vary with the type of hydrogenation
process, i.e., gas-phase hydrogenation/electrochemical
hydrogenation [222]. The values of hydrogen diffusion
coefficient of the alloy electrodes determined by various
electrochemical techniques are not exactly the same. In
addition to the uncertainty or inaccuracy of some parameters
used in these techniques as a cause, this is mainly due to the
fact that each technique has its own essential conditions and
proper application conditions, and different implications were
made during the deduction of the formulae for calculation of
the D H value in individual technique. This makes some
difference between these techniques. Sometimes, even the
results for the same alloy determined using same method are
quite different.
The electrochemical behavior of such intermetallics
depends on their structure, the nature and amount of each
element in the intermetallic compound, and the
electrochemical process(es) taking place. High exchange
current density and high hydrogen diffusivity in the bulk of
J Solid State Electrochem (2014) 18:577–593 589

Table 4 Values of hydrogen

diffusion coefficient for a number Alloys SOC (%) D H (cm2 s−1) Method References
of hydrogen storage alloys
LaNi3.55Mn0.4Al0.3Co0.4Fe0.35 0 0.57×10−11 EIS our work [216]
40 1.38×10−11
100 1.33×10−11
7 0.639×10−11 CPD our work [224]
60 2.999×10−11
100 3.069×10−11
LaNi4.27S0.24 0 3.851×10−11 CPD [27]
45 1.671×10−10
MlNi3.65Co0.75Mn0.4Al0.2 10 1.97×10−7 CV [221]
60 1.09×10−8
100 5.75×10−9
LaNi4.15Co0.43Mn0.40Fe0.02 100 2.53×10−11 CPD [211]
Mn0.95Ti0.05Ni3.85Co0.45Mn0.35Al0.35 100 1.2×10−11 A. polarization [239]
LaNi5 – 5×10−6 NMR [240]
PrNi3 100 4.51×10−10 CPD [219]
LaNi3 100 6.27×10−10
YNi3 100 14.69×10−10
Ti0.9Zr0.2Mn1.5Cr0.3 V0.3–x 100 0.62×10−14 (x =0), CPD [241]
wt%La0.7 Mg0.25Zr0.05Ni2.975Co0.525 1.58×10−14
(x =0, 5, 10) (x =5), 2.70×10−14
(x =10)
La2Mg(Ni0.95Al0.05)9 100 1.18×10−10 CPD [142]
La2Mg(Ni0.95Sn0.05)9 100 7.57×10−10
Ti0.9Zr0.2Mn1.5Cr0.3 V0.3 100 0.62×10−14 CPD [242]
TiCr1.85 – 3.1×10-8 QNS [243]
– 3.4×10−8 NMR
Ti0.9Zr0.1Mn1.6Ni0.4 100 4.3×10−11 CPD [244]
Ti0.8Zr0.2Mn1.6Ni0.4 100 4.3×10−11

the alloy are needed for improved performance of a metal
hydride electrode. These characteristics can be changed by
designing the composition of the hydrogen storage alloy to
provide optimum performance of the Ni=MH. Hydrogen
diffusivity in the alloy and exchange current density should
be high to ensure the high discharge rate of the Ni=MH
battery, especially at high discharge current densities. These
parameters are related to the mass transfer and charge transfer
processes, and the dischargeability of the battery depends
critically on these processes. Hydrogen diffusivity in the bulk
of alloys and exchange current density affect the rate at which
energy can be stored in, and also removed from, the Ni=MH
battery. The electrocatalytic activity, which is reflected by the
exchange current density, is hardly influenced by the chemical
composition and the surface properties of the electrode such as
oxide thickness, electrical conductivity, surface porosity and
topology, surface area, and degree of catalytic activity.
Conclusions
A large number of hydrogen storage alloys have been
developed as negative electrode materials for Ni/MH batteries.
Their performances differ greatly in terms of specific capacity,
activation, rate dischargeability, and cyclic lifetime. There is
an apparent trend to concentrate on low cost, light weight, and
excellent charge–discharge properties. These characteristics
can be changed by designing the composition of the hydrogen
storage alloy to provide optimum performance of the Ni/MH
batteries. The electrochemical behavior of such intermetallics
depends on the types of intermetallics, microstructure, the
nature and amount of each element in the intermetallic
compound, and the electrochemical process(es) taking place.
In this review, we present some recent results on the
electrochemical behavior of such compounds and the
mechanisms of the electrochemical reactions. At the present
time, Co-free hydrogen storage alloy has got attention and
there are some studies on it in recent years. Until now, AB5-
type hydrogen storage alloys are still one of the main choices
in commercial Ni/MH battery industry and lots of efforts are
made on cutting off their raw materials costs. Besides the cost
issue, Fe is an interesting substitution element inAB5 MH
alloys due to its atomic radius, number of electrons, and
electronegativity being similar to those of Ni and Co.
Recently, most of the Fe substitution in rare-earth-based AB5
MH alloys are for the purpose of replacing expensive Co.
590
In the search for new metal hydrides, recent attention has
been dedicated to the family of AB3- or A2B7-type rare earth–
magnesium-based alloys because their electrochemical
discharge capacities (about 400 mAh g−1) are higher than
AB5-type alloys. Now, the main problem for this series of
alloys to be used for industrialization is the poor cyclic
stability. It is well known that element substitution is one of
the effective methods for improving the overall properties of
the hydrogen storage alloys. At present, LaMgNiCo-based
alloys showed promising future for practical applications.
But the high cost is still an obstacle to their wide applications.
To reduce the alloy's cost, Co-free hydrogen storage alloy has
got attention and there are some studies on it. The results are
still quite incomplete.
The performance of a metal hydride electrode is
determined by the kinetics of the processes occurring at the
metal–electrolyte interface and the rate of hydrogen diffusion
within the bulk of the alloy. The exchange current density and
hydrogen diffusion coefficient are the most important kinetic
parameters that could significantly affect the performance of
Ni–MH rechargeable batteries. Their values for a number of
hydrogen storage alloys are compared. The differences in the
results can be attributed to differences in composition and in
the characteristics of the electrode reactions such as state of
charge, cycle, temperature, and surface modification.
Acknowledgments The authors wish to thank the reviewers for the
helpful comments and careful revision of the manuscript.
References
1. Zhan F, Jiang LJ, Wu BR, Xia ZH, Wei XY, Qin GR (1999) J Alloys
Compd 293:804–808
2. Yang XG, Liaw BY (2001) J Power Sources 101:158–166
3. Tliha M, Mathlouthi H, Khaldi C, Lamloumi J, Percheron-guegan
A (2006) J Power Sources 160:1391–1394
4. Jurczyk M, Rajewski W, Majchrzycki W, Wojcik G (1999) J Alloys
Compd 290:262–266
5. Willems JJG, Buschow KHJ (1987) J Less-Common Met 129:13–30
6. Sakai T, Miyamura H, Kuriyama N, Kato A, Oguro K, Ishikawa H
(1990) J Electrochem Soc 137:795–799
7. Pan HG, Ma JX, Wang CS, Chen CP, Wang QD (1999) Electrochim
Acta 44:3977–3987
8. Latroche M, Chabre Y, Percheron-Guegan A, Isnard O, Knop B
(2002) J Alloys Compd 330:787–791
9. Anani A, Visintin A, Srinivasan S, Appleby AJ, Lim HS (1992) J
Electrochem Soc 139:985–988
10. Pan HG, Chen Y, Wang CS, Ma JX, Chen CP, Wang QD (1999)
Electrochim Acta 44:2263–2269
11. Ovshinsky SR, Fetcenko MA (1993) J Ross Science 260:176–181
12. Zhang Y, Chen LX, Lei YQ, Wang QD (2002) Electrochim Acta 47:
1739–1746
13. Tian QF, Zhang Y, Sun LX, Xu F, Tan ZC, Yuan HT, Zhang T
(2006) J Power Sources 158:1463–1471
14. Tsukahara M, Kamiya T, Takahashi K, Kawabata A, Sakurai S, Shi
J, Takeshita N, Kuriyama HT, Sakai T (2000) J Electrochem Soc
147:2941–2944
J Solid State Electrochem (2014) 18:577–593
15. Lei YQ, Wu YM, Yang QM, Wu J, Wang QD (1994) Z Phys Chem
183:379–384
16. Iwakura C, Nohara S, Inoue H, Fukumoto Y (1996) Chem Commun
15:1831–1832
17. Bai T, Han S, Zh X, Zhang Y, Li Y, Zhang W (2009) Mater Chem
Phys 117:173–177
18. Li Y, Han S, Li J, Zhu X, Hu L (2008) J Alloys Compd 458:357–362
19. Ma J, Pan H, Zhu Y, Li S, Chen C, Wang Q (2001) Electrochem
Acta 46:2427–2434
20. Ye H, Huang YX, Huang TS, Zhang H (2002) J Alloys Compd 330:
866–870
21. Wang MH, Zhang Y, Zhang LZ, Sun LX, Tan ZC, Xu F, Yuan HT,
Zhang T (2006) J Power Sources 159:159–162
22. Khaldi C, Mathlouthi H, Lamloumi J, Percheron-Guegan J (2004) J
Int J Hydrogen Energy 29:307–311
23. Ratnakumar BV, Withan C, Bowman RC, Hightower A, Fultz B
(1996) J Electrochem Soc 143:2578–2584
24. Zheng G, Popov BN, White RE (1996) J Electrochem Soc 143(3):
834–839
25. Ciureanu M, Moroz D, Ducharme R et al (1994) Z Phys Chem Bd
183:365–370
26. Strom-Olsen JO, Zhao Y, Ryan DH (1991) J Less-Common Met
172:922–927
27. Haran BS, Popov BN, White RE (1998) J Power Sources 75:56–63
28. Kuriyama N, Sakai T, Miyamura H, Uehara I, Ishikawa H, Iwasaki
H (1992) J Electrochem Soc 139:L72–L73
29. Zhang W, Kumar MP, Srinivasan S, Ploehn HJ (1995) J
Electrochem Soc 142:2935–2943
30. Koura N, Takeda N, Kawashima K, Idemoto Y (1998) Denki
Kagaku Oyobi Kogyo Butsuri Kagaku 66:1135–1140
31. Ticianelli EA, Mukerjee S, McBreen J, Adzic GD, Johnson JR,
Reilly JJ (1999) J Electrochem Soc 146:3582–3590
32. Züttel A, Güther V, Otto A, Bärtsch M, Kötz R, Chartouni D,
Nützenadel CH, Schlapbach L (1999) J Alloys Compd 293:663–669
33. Yuan A, Xu N (2001) J Alloys Compd 322:269–275
34. Khaldi C, Mathlouthi H, Lamloumi J (2009) J Alloys Compd 479:
284–289
35. Wang C (1998) J Electrochem Soc 145(6):1801–1812
36. Yang H, Zhang Y, Zhou Z, Wei J, Wang G, Song D, Cao X, Wang C
(1995) J Alloys Compd 231:625–630
37. Baddour-Hadjean R, Mathlouthi H, Pereira-Ramos JP, Lamloumi J,
Latroche M, Percheron-Guegan A (2003) J Alloys Compd 356:
750–754
38. Ramya K, Rajalakshmi N, Sridhar P, Sivasankar B (2003) J Alloys
Compd 352:315–324
39. Muruganantham R, Rajalakshmi N, Dhathathreyan KS,
Ramaprabhu S (2003) J Power Sources 114:352–356
40. Lim C, Pyun SI (1993) Electrochim Acta 38:2645–2652
41. Zheng G, Haran BS, Popov BN, White RE (1999) J Appl
Electrochem 29:361–369
42. Li X, Dong H, Zhang A, Wie Y (2006) J Alloys Compd 426:93–96
43. Deng C, Shi P, Zhang P (2006) Mater Chem Phys 98:514–518
44. Wang Y, Lu ZW, Wang YL, Yan TY, Qu JQ, Gao XP, Shen PW
(2006) J Alloys Compd 421:236–239
45. Gao X, Liu J, Ye S, Song D, Zhang Y (1997) J Alloys Compd 253:
515–519
46. Gao XP, Zhang W, Yang HB, Song DY, Zhang YS, Zhou ZX, Shen
PW (1996) J Alloys Compd 235:225–231
47. Kuriyama N, Sakai T, Miyamura H, Uehara I, Ishikawa H (1993) J
Alloys Compd 192:161–163
48. Zheng G, Popov BN, White RE (1997) J Appl Electrochem 27:
1328–1332
49. Zheng G, Popov BN, White RE (1998) J Appl Electrochem 28:381–385
50. Lasia A, In: White RE, Conway BE, Bockris JOM (eds) (1999)
Modern aspects of electrochemistry 32. Kluwer Academic/Plenum,
New York, p 143
J Solid State Electrochem (2014) 18:577–593
51. Boukamp BA (1990) Equivalent circuits. Twente University of
Technology, Enschede
52. ZVIEW (1993) Impedance/gain phase graphics and analysis
software. Scribner Associates, Charlottesville
53. Zoltowski P (1998) J Electroanal Chem 443:149–154
54. Sadkowski A (2000) J Electroanal Chem 481:222–226
55. Láng G, Heusler KE (2000) J Electroanal Chem 481:227–229
56. Zoltowski P (2000) J Electroanal Chem 481:230–231
57. Brug GJ, Van Den Eeden ALG, Sluyters-Rehbach M, Sluyters JH
(1984) J Electroanal Chem 176:275–295
58. Ross Macdonald J (1987) Impedance spectroscopy: emphasizing
solid materials and analysis. Wiley, New York
59. Singh SK, Ramakrishna K, Singh AK, Srivastava ON (1989) Int J
Hydrogen Energy 14:573–577
60. Pandey SK, Srivastava A, Srivastava ON (2007) Int J Hydrogen
Energy 32:2461–2465
61. Singh RK, Lototsky MV, Srivastava ON (2007) Int J Hydrogen
Energy 32:2971–2976
62. Zhang J, Zhou DW, He LP, Peng P, Liu JS (2009) J Phys Chem
Solids 70:32–39
63. Zhang XZ, Yang R, Qu JL, Zhao W, Xie L, Tian WH, Li X (2010)
Nanotechnology 21:095706
64. Bernauer O, Topler J, Noreus D, Hempelmann R, Richter D (1989)
Int J Hydrogen Energy 14:187–200
65. Reilly JJ Jr, Wiswall RH (1974) Inorg Chem 13:218–222
66. Gennari FC, Urretavizcaya G, Gamboa JJA, Meyer GJ (2003)
Alloys Compd 354:187–192
67. Yoshida M, Akiba E (1995) J Alloys Compd 224:121–126
68. Bobet JL, Chevalier B, Darriet B (2000) Intermetallics 8:359–363
69. Chen J, Takeshita TH, Tanaka H, Kuriyama N, Sakai T, Uehara I,
Haruta M (2000) J Alloys Compd 302:304–313
70. Ivey DG, Northwood DO (1983) J Mater Sci 18:321–347
71. Shaltiel D (1978) J Less-Common Met 62:407–416
72. Young K, Fetcenko MA, Li F, Ouchi T (2008) J Alloys Compd 464:
238–247
73. Young K, Fetcenko MA, Li F, Ouchi T, Koch J (2009) J Alloys
Compd 468:482–492
74. Young K, Fetcenko MA, Ouchi T, Li F, Koch J (2009) J Alloys
Compd 469:406–416
75. Young K, Ouchi T, Koch J, Fetcenko MA (2009) J Alloys Compd
477:749–758
76. Yu JS, Lee SM, Cho K, Lee JY (2000) J Electrochem Soc 147:
2013–2017
77. Young K, Ouchi T, Fetcenko MA (2009) J Alloys Compd
476:774–781
78. Young K, Ouchi T, Mays W, Reichman B, Fetcenko MA (2009) J
Alloys Compd 480:434–439
79. Yong K, Fetcenko MA, Khoch J, Morii K, Shimizu T (2009) J
Alloys Compd 486:559–569
80. Shaltiel D, Jacob I, Davidov D (1977) J Less-Common Met
53:117–131
81. Honda N, Furukawa N, Fujitani S, Yonezu I (1990) US Patent
4913879
82. Kim S, Lee J (1994) J Alloys Compd 210:109–113
83. Nakano H, Wakao S (1995) J Alloy Compd 231:587–593
84. Chen J, Dou SX, Liu HK (1997) J Alloys Compd 256:40–44
85. Pebler A, Gulbransen EA (1966) Electrochem Technol 4:211–215
86. Kim D, Jang K, Lee J (1999) J Alloys Compd 293:583–592
87. Zuttel A, Fischer P, Fauth F, Otto A, Guther V (2002) J Alloys
Compd 333:99–102
88. Lupu D, Biris AR, Biris AS, Indrea E, Misan I, Zuttel A,
Schlapbach L (2003) J Alloys Compd 350:319–323
89. Gao X, Song D, Zhang Y, Wang G, Shen P (1995) J Alloys Compd
223:77–80
90. Cui X, Li Q, Chou K, Chen S, Lin G, Xu K (2008) Intermetallics 16:
662–667
591
91. Gao XP, Ye SH, Liu J, Song DY, Zhang YS (1998) Int J Hydrogen
Energy 23:781–786
92. Shu K, Zhang S, Lei Y, Lu G, Wang Q (2003) J Alloys Compd 349:
237–241
93. Pan H, Zhu Y, Gao M, Wang Q (2002) J Electrochem Soc 149:
A829–A833
94. Zhu Y, Pan H, Gao M, Liu Y, Wang Q (2003) J Alloys Compd 348:
301–308
95. Lakner JF, Uribe FS, Steward SA (1980) J Less-Common Met 72:
87–105
96. Wallace WE, Kalicek RF, Imamura H (1979) J Phys Chem 83:
1708–1712
97. Sakai T, Miyamura H, Kuriyama N, Kato A, Oguro K, Ishikawa H
(1990) J Less-Common Met 159:127–139
98. Sakai T, Yoshinaga H, Miyamura H, Kuriyama N, Ishikawa H
(1992) J Alloy Compd 180:37–54
99. Pan HG, Ma JX, Wang CS, Cheng SA, Wang XH, Chen CP, Wang
QD (1999) J Alloys Compd 293:648–652
100. Hu WK, Le H, Kim DM, Jeon SW, Lee JY (1998) J Alloys Compd
268:261–265
101. Notten PHL, Latroche M, Percheron-Guegan A (1999) J
Electrochem Soc 146:3181–3189
102. D Maziére (2002) J Phys IV France 12 :Pr2-III
103. Ogawa H, Ikoma M, Kawano H, Matsumoto I (1988) J Power
Sources 12:393–410
104. Ikoma M, Kawano H, Matsumoto I, Yanagihara N (1987) Eur Pat
No. 0271043
105. Huang YX, Zhang H (2000) J Alloys Compd 305:76–81
106. Hu WK (1999) J Alloys Compd 289:299–305
107. Hu WK (2000) J Alloys Compd 297:206–210
108. Wang Y, Yuan H, Wang G, Zhang Y (2002) Solid State Ionics 148:
509–512
109. Tang R, Zhang ZH, Liu LQ, Liu YN, Zhu JW, Yu G (2004) Int J
Hydrogen Energy 29:851–858
110. Yuexiang H, Hong Z (2000) J Alloys Compd 305:76–81
111. Tang R, Liu L, Liu Y, Yu G (2003) Int J Hydrogen Energy
28:815–819
112. Chartouni D, Meli F, Züttel A, Gross K, Schlapbach L (1996) J
Alloys Compd 241:160–166
113. Mao LC, Shan ZQ, Yin SH, Liu B, Wu F (1999) J Alloys Compd
293:825–828
114. Sakai T, Oguro K, Miyamura H, Kuriyama N, Kato A, Ishikawa H
(1990) J Less-Common Met 161:193–202
115. Adzic GD, Johnson JR, Mukerjee S, Breen JM, Reilly JJ (1997) J
Alloys Comp 253:579–582
116. Tang W, Gai Y, Zheng H (1995) J Alloys Compd 224:292–298
117. Weizhong T, Yinxin G, Haoyu Z (1995) J Appl Electrochem 25:
874–880
118. Ma JX, Pan HG, Yu G, Chen CP, Wang QD (2002) J Alloys Compd
343:164–169
119. Tang R, Zhang Z, Liu L, Liu Y, Zhu J, Yu G (2004) Int J Hydrogen
Energy 29:851–858
120. Wei XD, Liu YN, Yu G, Zhu JW (2006) J Alloys Compd
414:253–258
121. Zhang YH, Chen MY, Wang XL, Wang GQ, Lin YF, Qi Y (2004) J
Power Sources 125:273–279
122. Zuttel A, Chartouni D, Gross K et al (1997) J Alloys Compd 253:
626–628
123. Hasegawa K, Ohnishi M, Oshitani M, Takeshima K, Matsumaru Y
(1994) Z Phys Chem Bd 183:325–331
124. Cocciantelli JM, Bernard P, Fernandez S, Atkin J (1997) J Alloys
Compd 253:642–647
125. Iwakura C, Ohkawa K, Senoh H, Inoue H (2001) Electrochim Acta
46:4383–4388
126. Chen XL, Lei YQ, Liao B, Wei FS, Chen LX (2004) Chin J
Nonferrous Metals 14:1862–1868
592
127. Vivet S, Jouber JM, Knosp B, Percheron-Guegan A (2003) J Alloys
Compd 356:779–783
128. Zhang YH, Wang GQ, Dong XP, Guo SH, Ren JY, Wang XL (2005)
J Power Sources 148:105–111
129. Zhang Y, Dong X, Wang G, Guo S, Wang X (2005) J Power Sources
140:381–387
130. Zhao Y, Zhang Y, Wang G, Dong X, Guo S, Wang X (2005) J
Alloys Compd 388:284–292
131. Tliha M, Mathlouthi H, Khaldi C, Lamloumi J, Percheron-Guégan
A (2006) J Power Sources 160:1391–1394
132. Moussa MB, Abedellaoui M, Mathlouthi H, Lamloumi J,
Percheron-Guégan A (2006) J Alloys Compd 407:256–262
133. Ayari M, Paul-Boncour V, Lamloumi J, Percheron-Guégan A
(2002) J Magn Magn Mater 242:850–853
134. Ayari M, Paul-Boncour V, Lamloumi J, Percheron-Guégan A,
Guillot M (2005) J Magn Magn Mater 288:374–383
135. Moussa MB, Abedellaoui M, Mathlouthi H, Lamloumi J,
Percheron-Guégan A (2008) J Alloys Compd 458:410–414
136. Kadir K, Sakai T, Uehara I (1997) J Alloys Compd 257:
115–121
137. Kadir K, Kuriyama N, Sakai T, Uehara I, Eriksson L (1999) J Alloys
Compd 284:145–154
138. Kadir K, Sakai T, Uehara I (1999) J Alloys Compd 287:
264–270
139. Kadir K, Sakai T, Uehara I (2000) J Alloys Compd 302:112–117
140. Liu YF, Pan HG, Gao MX, Li R, Lei YQ (2004) J Alloys Compd
376:304–313
141. Zhang YH, Li BW, Ren HP, Cai Y, Dong XP, Wang XL (2008) J
Alloys Compd 458:340–345
142. Liao B, Lei YQ, Chen LX, Lu GL, Pan HG, Wang QD (2004) J
Alloys Compd 376:186–195
143. Zhang YH, Li BW, Ren HP, Wu ZW, Dong XP, Wang XL (2008) J
Alloys Compd 461:591–597
144. Zhang YH, Li BW, Ren HP, Guo SH, Qi Y, Wang XL (2009) J
Alloys Compd 485:333–339
145. Shen X, Chen Y, Tao M, Wu C, Deng G, Kang Z (2009) Int J
Hydrogen Energy 34:2661–2669
146. Zhang YH, Li BW, Ren HP, Cai Y, Dong XP, Wang XL (2007) Int J
Hydrogen Energy 32:4627–4634
147. Zhang YH, Li BW, Ren HP, Wu ZW, Dong XP, Wang XL (2008) J
Alloys Compd 460:414–420
148. Bai TY, Han SM, Zhu XL, Zhang Y, Li Y, Zhang WC (2009) Mater
Chem Phys 117:173–177
149. Zhang YH, Dong XP, Zhao DL, Guo SH, Qi Y, Wang XL (2008)
Trans Nonferrous Metals Soc China 18:857–864
150. Kohno T, Yoshida H, Kawashima F, Inaba T, Sakai I, Yamamoto M,
Kanda M (2000) J Alloys Compd 311:L5–L7
151. Zhnag XB, Sun DZ, Yin WY, Chai YJ, Zhao MS (2005)
Electrochim Acta 50:1957–1964
152. Zhang YH, Wang GQ, Dong XP, Guo SH, Ren JY, Wang XL (2006)
Rare Metal Mater Eng 35:277–282
153. Cheng LF, Wang RB, Pu CH, Wang BG, Li ZL, Luo YW, He DN,
Yang CZ (2009) Rare Metal Mater Eng 38:451–455
154. Wei XD, Zhang P, Dong H, Liu YN, Zhu JW, Yu G (2008) J Alloys
Compd 458:583–587
155. Wei XD, Liu SS, Dong H, Zhang P, Liu YN, Zhu JW, Yu G (2007) J
Electrochim Acta 52:2423–2428
156. Guo J, Yang K, Xu LQ, Liu YX, Zhou KW (2007) J Hydrogen
Energy 32:2412–2416
157. Shao H, Asano K, Enoki H, Akiba E (2009) J Alloys Compd 479:
409–413
158. Zhao X, Ma L (2009) Int J Hydrogen Energy 34:4788–4796
159. Bououdina M, Grant D, Walker G (2006) Int J Hydrogen Energy 31:
177–182
160. Buschow KHJ, Bouten PCP, Miedema AR (1982) Rep Prog Phys
45:937–1039
J Solid State Electrochem (2014) 18:577–593
161. Kleperis J, Wojcik G, Czerwinski A, Skowronski J, Kopczyk
M, Beltowska-Brzezinska M (2001) J Solid State Electrochem 5:
229–249
162. Abrashev B, Spassov T, Bliznakov S, Popov A (2010) Int J
Hydrogen Energy 35:6332–6337
163. Schlapbach L, Riesterer T (1983) Appl Phys A 32:169–182
164. Sandrock GD, Goodell PD (1984) J Less-Common Metals 104:
159–173
165. Schlapbach L (1992) Hydrogen in intermetallic compounds II. In:
Schlapbach L (ed) Topics in Appl. Phys. 67. Springer, Berlin, p 76
166. Sandrock G (1999) J Alloys Compd 293:877–888
167. Lee HH, Lee KY, Lee JY (1996) J Alloys Compd 239:63–70
168. Xu YH, Chen CP, Wang XL, Wang QD (2002) J Alloys Compd
335:262–265
169. Jurczyk M, Jankowska E, Nowak M, Jakubowicz J (2002) J Alloys
Compd 336:265–269
170. Cuevas F, Latroche M, Percheron-Guegan A (2005) J Alloys
Compd 404:545–549
171. Drenchev B, Spassov T (2007) J Alloys Compd 441:197–201
172. Szajek A, Jurczyk M, Jankowska E (2003) J AlloysCompd 348:
285–292
173. Cuevas F, Latroche M, Ochin P, Dezellus A, Fernandez JF, Sanchez
C et al (2002) J Alloys Compd 330:250–255
174. Drenchev B, Spassov T, Radev D (2008) J Appl Electrochem 38:
437–444
175. Wang CS, Lei YQ, Wang QD (1998) Electrochim Acta 43:
3193–3207
176. Wang CS, Lei YQ, Wang QD (1998) J Power Sources 70:222–227
177. Westlake DG (1983) J Less-Common Met 90:251–273
178. Stetson NT, Yvon K, Fischer P (1994) Inorg Chem 33:4598–4599
179. Joubert JM, Cerny R, Latroche M, Percheron-Guegan A, Yvon K
(2005) Intermetallics 13:227–231
180. Bliznakov S, Lefterova E, Bozukov L, Popov A, Andreev P (2004)
Proceedings of the International Workshop “Advanced Techniques
for Energy Sources Investigation and Testing”, September 4–9,
Sofia, Bulgaria
181. Zhang RJ, Lu MQ, Chen DM, Yang K (2005) Acta Metall Sinica
41:427–432
182. Hong k (1991) Method for preparing materials for hydrogen storage
and for hydride electrode applications, US patent 5,006,328
183. Sastri MVC (ed) (1998) Metal hydrides: Fundamentals and
applications. Narosa, New Delhi
184. Hagstrom MT, Vanhanen JP, Lund PD (1998) J Alloys Compds
269:288–293
185. Hagstrom MT, Klyamkin SN, Lund PD (1999) J Alloys Compds
293:67–73
186. Kapischke J, Hapke J (1998) Exp Therm Fluid Sci 18:70–81
187. Puszkiel JA, Arneodo Larochette P, Gennari FC (2008) Int J
Hydrogen Energy 33:3555–3560
188. Singh RK, Lototsky MV, Srivastava ON (2007) Int J Hydrogen
Energy 32:2971–2976
189. Feng F, Geng M, Northwood DO (2002) Comput Mater Sci 23:
291–299
190. Giza K, Iwasieczko W, Pavlyuk VV, Bala H, Drulis H (2008) J
Power Sources 181:38–40
191. Laurencelle F, Dehouche Z, Goyette J (2006) J Alloys Compds 424:
266–271
192. Kandavel M, Bhat VV, Rougier A, Aymard L, Nazri GA, Tarascon
JM (2008) Int J Hydrogen Energy 33:3754–3761
193. Anil Kumar E, Prakash Maiya M, Srinivasa Murthy S (2007) Int J
Hydrogen Energy 32:2382–2389
194. Yamaguchi M, Akiba E (1994) Ternary hydrides. In: Buschow KHJ
(ed) Electronic and magnetic properties of metals andceramics part
II. Wiley, New York, pp 334–398
195. Bliznakov S, Lefterova E, Bozukov L, Popov A, Andreev P (2004)
Proceedings of the International Workshop “Advanced Techniques
J Solid State Electrochem (2014) 18:577–593 593

for Energy Sources Investigation and Testing”, September 4–9, 220. Iwakura C, Oura T, Inoue H, Matsuoka M, Yamamoto Y (1995) J
Sofia, Bulgaria Electroanal Chem 398:37–41
196. Schlapbach L (1988) Hydrogen in intermetallic compounds I 63: 221. Yuan X, Xu N (2001) J Alloys Compd 316:113–117
350. Springer, Berlin 222. Yuan X, Xu N (2001) J Alloys Compd 329:115–120
197. Jordy C, Percheron-Guegan A, Bouet J, Sanchez P, Chanson C, 223. Yuan X, Ma ZF, Nuli Y, Xu N (2004) J Alloys Compd 385:90–95
Leonardi J (1991) J Less-Common Met 172:1236–1245 224. Tliha M, Mathlouthi H, Lamloumi J, Percheron-Guégan (2007) J
198. Young K, Chao B, Bendersky LA, Wang K (2012) J Power Sources Alloys Compd 436:221–225
218:487–494 225. Zhou ZX, Huang JS, Hu WK, Yao FY, Zhang YS (1995) J Alloys
199. Balasubramaniam R (1997) J Alloys Compd 253:203–206 Compounds 231:297–301
200. Inui H, Yamamoto T, Hirota M, Yamaguchi M (2002) J Alloys 226. Yang XG, Liaw BY (2001) J Power Sources 102:186–197
Compd 330:117–124 227. Ciureanu M, Ryan DH, Strom-Olsen JO, Trudeau ML (1993) J
201. Kisi EH, Buckley CE, Gray EM (1992) J Alloys Compd 185:369–384 Electrochem Soc 140:579–584
202. Wu E, Kisi EH, Maca Gray E (1998) J Appl Crystallogr 31:363–368 228. Karlicek RF Jr, Lowe IJ (1980) J Less-Common Met 73:219–225
203. Adzic G, Johnson JR, Reilly JJ, McBreen J, Mukerjee S, 229. Zuchner H, Hempelmann TR (1991) J Less-Common Met 172:
Kumar MPS, Zhang W, Srinivasan S (1995) J Electrochem 611–617
Soc 142:3429–3433 230. Wang XL, Suda S (1992) Int J Hydrogen Energy 17:139–147
204. Peng CH, Zhu M (2004) J Alloys Compd 375:324–329 231. Wang CS, Wang XH, Lei YQ, Chen CP, Wang QD (1996) Int J
205. Young K, Ouchi T, Fetcenko MA (2009) J Alloys Compd Hydrogen Energy 21:471–478
480:428–433 232. Zhang W, Srinivasan S, Ploehn HJ (1996) J Electrochem Soc 143:
206. Young K, Ouchi T, Fetcenko MA (2009) J Alloys Compd 4039–4047
480:440–448 233. Wicke E, Brodowsky H (1978) Hydrogen in palladium alloys
207. Osumi Y, Suzuki H, Kato A, Oguro K, Kawai S, Kaneko M (1983) J (chapter 3). In: Alefeld G, Volkl J (eds) Hydrogen in metals II,
Less-Common Met 89:287–292 application oriented properties, topics in applied physics (vol. 29).
208. Mungole MN, Balasubramaniam R, Rai KN (1995) Int J Hydrogen Springer, Berlin
Energy 20:151–157 234. Yuan X, Xu N (2001) J Appl Electrochem 31:1033–1039
209. Gamo T, Moriwaki Y, Yanagihara N, Yamashita T, Iwaki T (1985) 235. Feng F, Han J, Geng M, Northwood DO (2000) J Electroanal Chem
Int J Hydrogen Energy 10:39–47 487:111–119
210. Moriwaki Y, Gamo T, Iwaki T (1991) J Less-Comm Met 236. Feng F, Northwood DO (2004) J Power Sources 136:346–350
172:1028–1035 237. Kim HS, Nishizawa M, Uchida I (1999) Electrochim Acta
211. Popović MM, Grgur BN, Vojnović MV, Rakin P, Krstajić NV 45:483–488
(2000) J Alloys Compd 298:107–113 238. Iwakura C, Fukuda K, Senoh H, Inoue H, Matsuoka M, Yamamoto
212. Witham C, Fultz B, Ratnakumar BV, Bowman RC, Hightower A Y (1998) Electrochim Acta 43:2041–2046
(1997) J Electrochem Soc 144:3758–3764 239. Geng M, Han J, Feng F, Matchett AJ, Northwood DO (1999) J New
213. Wang CS, Soriaga MP, Srinivasan S (2000) J Power Sources 85: Mat Electrochem Systems 2:261–265
212–223 240. Khodosov E, Linnik A, Kobsenko G, Ivanchenko V (1977) In:
214. Zheng G, Popov BN, White RE (1996) J Electrochem Soc 143:435–441 Proceedings of the 2nd international congress on ‘Hydorgen in
215. Popov BN, Zheng G, White RE (1996) J Appl Electrochem metals’, (Paris). Pergamon, Oxford, paper 1D10
26:603–611 241. Chu HL, Zhang Y, Sun LX, Qiu SJ, Xu F, Yuan HT (2007) Int J
216. Tliha M, Boussami S, Mathlouthi H, Lamloumi J, Percheron- Hydrogen Energy 32:1898–1904
Guégan A (2010) J Alloys Compd 506:559–564 242. Chu H, Zhang Y, Sun L, Qiu S, Qi Y, Xu F, Yuan H (2007) J Alloys
217. Tliha M, Mathlouthi H, Lamloumi J, Percheron-Guégan (2007) Int J Compd 446:614–619
Hydrogen Energy 32:611–614 243. Campbell SI, Kemali M, Ross DK, Bull DJ, Fernandez JF, Johnson
218. Verbetsky VN, Petrii OA, Vasina SY, Bespalov AP (1999) Int J MR (1999) J Alloys Compd 293:351–355
Hydrogen Energy 24:247–249 244. Ramya K, Rajalakshmi N, Sridhar P, Sivasankar B (2004) J Alloys
219. Zhang X, Yin W, Chai Y, Zhao M (2005) Mater Sci Eng B 117:123–128 Compd 373:252–259