Materials Chemistry and Physics 200 (2017) 164e178

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Progress of hydrogen storage alloys for Ni-MH rechargeable power

batteries in electric vehicles: A review
Liuzhang Ouyang a, b, Jianling Huang a, b, Hui Wang a, b, Jiangwen Liu a, b, Min Zhu a, b, *
a
School of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of
Technology, Guangzhou, 510641, PR China
b
China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou, 510641, PR China

h i g h l i g h t s

The prerequisites for Ni-MH battery are summarized.

The Relationship between electrochemical performance and hydrogen storage properties are noted.

The relationship between alloying compositions, crystal structures and properties for each type alloy are narrated.

The achieved research results, existing problems and development direction are discussed.

a r t i c l e i n f o a b s t r a c t

Article history: As clean energy materials, hydrogen storage alloys have been widely investigated and applied as negative
Received 16 November 2016 electrodes for nickel-metal hydride (Ni-MH) rechargeable batteries due to their high energy densities
Received in revised form and environment-friendliness. This review details the progress made in the last few decades on
19 June 2017
hydrogen storage alloys, such as AB5-type alloys, AB2-type alloys, Mg-based alloys, Ti-V-based alloys and
Accepted 1 July 2017
RE-Mg-Ni (rare earth abbreviated as RE) alloys, for Ni-MH rechargeable batteries. The principles of Ni-
Available online 3 July 2017
MH batteries and the relationship between electrochemical performance and hydrogen storage prop-
erties have been narrated in detail. The achieved research results, existing problems and development
Keywords:
Electric vehicles
direction are discussed systematically. The relationship between alloying compositions, crystal structures
Ni-MH batteries and electrochemical properties for each alloy type are also noted and analyzed with the emphasis on
Hydrogen storage alloys power batteries. Finally, the challenges of Ni-MH batteries are discussed in the context of developing
Electrochemical properties electric vehicles.
© 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
2. Relationship between electrochemical performance and hydrogen storage properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . 166
3. Main hydrogen storage alloys for Ni-MH batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
3.1. AB5-type hydrogen storage alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
3.2. AB2-type alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
3.3. A2B7-type and AB3-type RE-Mg-Ni-based superlattice alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
3.4. Ti-V-based alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
3.5. Co-based alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
3.6. Mg-based alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174

* Corresponding author. School of Materials Science and Engineering, Key Lab-

oratory of Advanced Energy Storage Materials of Guangdong Province, South China
University of Technology, Guangzhou, 510641, PR China.
E-mail address: memzhu@scut.edu.cn (M. Zhu).

http://dx.doi.org/10.1016/j.matchemphys.2017.07.002
0254-0584/© 2017 Elsevier B.V. All rights reserved.

4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
1. Introduction
With increasing energy demand, the consumption of fossil fuels,
such as coal, oil and natural gas, has become a serious burden to the
environment and energy resources [1]. Therefore, it is essential to
develop new green energies and energy saving technologies.
Developing clean electric vehicles (EVs), fuel-efficient hybrid elec-
tric vehicles (HEVs) and distributed energy storage stations is an
appropriate approach to ease these problems, and reliable batte-
ries, as power conversion and storage devices, play a key role [2].
Several types of rechargeable batteries, such as lead (Pb)-acid
batteries, nickel-cadmium (Ni-Cd) batteries, nickel-metal hydride
(Ni-MH) batteries and lithium (Li)-ion batteries, have been devel-
oped and practically applied [3,4]. Among them, as shown in Fig. 1
[3] and Table 1 [5], Li-ion batteries have relatively higher energy
density, but as an energy carrier for electric vehicles, they are still a
safety hazard. Ni-MH batteries have high power capability, toler-
ance to overcharge/discharge, environmental compatibility and
safety, which make them appropriate for portable power tools and
HEVs, although their energy density is relatively low compared to
Li-ion batteries [6].
A Ni-MH battery consists of a metal hydride (MH) negative
electrode, a Ni(OH)2 positive electrode and an alkaline electrolyte
(KOH). Fig. 2(a) shows the principles of a Ni-MH battery. The
electrochemical reactions that occur for the charge-discharge
process in a Ni-MH battery are as follows [5e7]:
On positive electrode : NiðOHÞ2 þ OH )
þ H2 O þ e
On negative electrode : M þ H2 O þ e )
Charge
Overall reaction : NiðOHÞ2 þ M )
Discharge
When the battery is overcharged or overdischarged, the re-
actions occurring at the positive and negative electrodes can be
expressed as follows:
Overcharge on positive electrode : 4OH /2H2 O þ O2 þ 4e
On negative electrode : 2H2 O þ O2 þ 4e /4OH
4MH þ O2 /4M þ 2H2 O
Overall reaction : 4MH þ O2 /4M þ 2H2 O
Overdischarge on positive electrode
: 2H2 O þ 2e /H2 þ 2OH
L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178 165
On negative electrode : H2 þ 2OH /2H2 O þ 2e (1-9)
cH2 þ 2M/2MHc (1-10)
Overall reaction : cH2 þ 2M/2MHc (1-11)
Therefore, in general, the capacity of the negative electrode is
set higher than that of the positive electrode, and the oxygen
produced from the positive electrode can be reduced at the surface
of the MH electrode during the overcharge process (oxygen con-
sumption reaction). As for the overdischarge process, correspond-
ingly, the reduction product, hydrogen, is absorbed by the MH
electrode (hydrogen elimination reaction). Hence, Ni-MH batteries
exhibit excellent tolerability during the overcharge and over-
discharge processes.
The hydriding and dehydriding of electrodes involves a series of
reactions and mass transport [8,9], as illustrated in Fig. 2(b). It is
obvious that the hydrogen is supplied from the electrolyte. The H2O
dissociates into H(ad) and OH at the interface of the solid, and then,
H(ad) combines with the hydrogen storage alloys to form M-H(ad)
and the adsorbed hydrogen diffuses into the bulk of the alloys to
form a solid-solution phase (a phase). Finally, the a phase trans-
forms into a hydride phase with further increases in H concentra-
tion. The reverse reactions take place during the electrochemical
dehydriding reaction.
According to the principles of Ni-MH batteries and their oper-
Charge ating conditions, a hydrogen storage electrode alloy must satisfy
* NOOH
Discharge the following basic requirements [6,10e14]: (1) high reversible
hydrogen storage capacity and suitable absorption/desorption
plateau pressure, (2) good electrochemical catalysis for hydrogen
(1-1) absorption and desorption, and excellent electrochemical stability
in alkaline electrolyte, (3) good charge/discharge kinetics for effi-
Charge cient operation and long cycle life, (4) a wide working temperature
* MH þ OH
Discharge range and (5) resource-rich, cheap and easy to industrially produce.
The electrochemical performances of Ni-MH batteries strongly
(1-2)
depend on the intrinsic properties of the electrode materials. So far,
only a small number of hydrogen storage alloys, including AB5-type
* NOOH þ MH (1-3)
(1-4)
(1-5)
(1-6)
(1-7)
(1-8) Fig. 1. Comparison of the different battery technologies in terms of volumetric and
gravimetric energy density and some hydrogen storage materials [3].
166 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178

Table 1
Rechargeable batteries selected for application in electric vehicles [5].

Technology Environmental Nominal voltage (V) Costs ($/Wh) Specific energy (Wh/kg) Cycle life

Lead-acid Toxic 2.0 0.1e0.3 20e35 100e500

Ni-Cd Toxic 1.2 0.5e1.5 30e50 1000
Ni-MH Low toxicity 1.2 1.0 60e120 500
Lithium-ion Hazardous 1.5e3.9 0.2e0.3 115e265 400e1200

Fig. 2. Schematic diagram of the electrochemical reaction process of a Ni-MH battery (a) and the hydride formation/decomposition process occurring via electrochemical charge
transfer reaction (b) [6].

alloys, AB2-type alloys, Mg-based alloys, Ti-V-based alloys and
A2B7-type or AB3-type rare earth (RE)-Mg-Ni-based superlattice
alloys, have been developed as anode materials for Ni-MH batteries,
and significant efforts have been devoted to promote their elec-
trochemical properties, such as energy density, high rate discharge
ability (HRD) and cycle life.
The Ni-MH battery industry has undergone rapid development
since Japan began to produce Ni-MH batteries in large batches in
1990, and well-known battery manufacturers in several countries
have also accelerated the industrial development of Ni-MH batte-
ries. The gravimetric and volumetric energy densities of AA-size Ni-
MH cells have been raised from 54 to 110 Wh/kg and 190 to
490 Wh/L, respectively [15]. Their power has increased from under
200e1200 W/kg commercially, and up to 2000 W/kg at a devel-
opment level [16]. In 2000, the total output of small Ni-MH batte-
ries was up to 1 billion in Japan. China was one of the few countries
to participate in the early development of Ni-MH batteries. Since
1995, China has built a number of production bases for the large-
scale production of Ni-MH batteries, such as the Tianjin Peace
Bay Company, the Shenyang Sanpu Company, the Shenzhen BYD
Company, the Shenzhen HPJ Company and the Shenzhen Great
Power Company. Now, the production and export of Ni-MH batte-
ries in China are more than in Japan, meaning that China is ranked
first in the production of Ni-MH batteries in the world. The export
volume from China was 0.69 billion in 2012, 0.627 billion in 2013
and 0.573 billion in 2014 (Fig. 3). Due to the impact of the global
economic crisis and the rise of Li-ion batteries, the market for Ni-
MH batteries has been declining in recent years. At present, 85%
of the listed HEVs are based on Ni-MH batteries as power sources.
However, the requirements for energy density show an increasing
trend over time. In particular, with the rapid development of HEVs,
high power and a long cycle life are required for Ni-MH batteries.
Hence, efforts to improve the properties of Ni-MH batteries are still
ongoing.
Here, we detail the relationships between electrochemical per-
formances and properties of hydrogen storage alloys used as the
negative electrode in Ni-MH batteries, with the emphasis on how
the alloy compositions and crystal structures contribute to the
electrochemical properties of the main types of hydrogen storage
alloys. This review will provide a deeper understanding and
elucidate the challenges of hydrogen storage alloy anodes for Ni-
MH batteries and provide some references and enlightenment for
future research.

2. Relationship between electrochemical performance and

hydrogen storage properties

The most important electrochemical properties of hydrogen

storage alloys, with respect to practical applications, are activation
performance, maximum discharge capacity (Cmax), capacity reten-
tion rate and high rate dischargeability (HRD). In general, Cmax is
achieved after several charge-discharge cycles [17e19], and the
Fig. 3. The sales amount and export volume of Ni-MH batteries from 2012 to 2014 in cycle number (Na) to reach Cmax is related to the so-called activation
China. performance. Because of the dissolution of some elements in
 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178
alkaline solution, such as La and Mg, and pulverization caused by
expanding/contracting of the unit cell volume during the char-
geedischarge processes of alloys, the capacity decreases with
cycling. The capacity retention rate is calculated by the formula
x ¼ Cn =Cmax  100%, where Cn is the discharge capacity for the nth
cycle [20,21].
The electrochemical performance of MHs is determined by their
hydrogen storage capacity, kinetics and thermodynamic stability.
The thermodynamic properties are normally characterized by the
formation enthalpy (DH) and entropy (DS) of the hydride. Kleperis
at al. [5] stated that DH should range between 25
and 50 kJ mol1 for an alloy as a candidate for battery applica-
tions. The values for DH and DS can be derived from the pressure-
composition-isothermal (PCI) at different temperatures using the
van't Hoff equation [22]:
h . i
ln PH2 Pq ¼ DH=RT  DS=R
where PH2 is the equilibrium plateau pressure of the PCI, which is
usually determined by the mid-plateau values, and Pq is the stan-
dard pressure. As shown in Fig. 4 [10], the plateau region corre-
sponds to the saturated a phase transforming into the b phase in
the domain of amax to bmin in PCI curve. The electrode potential in
Ni-MH batteries is closely related to the plateau pressure of the PCI
and can be calculated by the Nernst equation [23,24]:
RT
Eeq ¼ E0  lnðPH2 Þ ¼ 0:9324  0:0291 lnðPH2 Þ
2F
where E0 ¼ 0.9324 V (vs. Hg/HgO) and F is the Faraday constant.
The theoretical electrochemical capacity of a hydrogen storage
alloy anode is determined by the H capacity in the plateau of the PCI
and can be calculated using Eqs. (2) and (3) derived from Faraday's
law, where F, CH and MW represent the Faraday constant, the atoms
per formula unit (H/f.u.) and the molecular weight of the alloy in g/
f.u., respectively.
F  CH
C ðmAh=gÞ ¼
3:6  MW
The electrochemical reaction kinetics are another important
factor that controls the electrochemical properties, especially the
HRD of Ni-MH batteries [5]. In general, the kinetics are mainly
Fig. 4. Typical PCT curves for hydrogen absorptionedesorption in intermetallic com-
pounds [10].
167
controlled by both the charge-transfer process on the electrode/
electrolyte interface and the hydrogen diffusivity within the bulk of
the alloy [10]. It is known that the electrochemical reactions inside
the hydrogen storage alloy electrodes are related to the mass
transfer, charge transfer and hydrogen diffusion processes. The
charge transfer and hydrogen diffusion occur simultaneously dur-
ing the charging/discharging processes of the alloy electrode, and
both of them limit the rate of electrode reactions. The charge
transfer process can be characterized by the charge-transfer resis-
tance (Rct) and the exchange current density (I0), and the hydrogen
diffusivity can be evaluated through the limiting current density (IL)
and hydrogen diffusion coefficient (D) [6,27]. Table 2 shows the
relationship of the HRD to the charge transfer rate and hydrogen
diffusivity for some representative compounds of each type of
hydrogen storage alloy. Obviously, the HRD is determined by both
the charge transfer rate and hydrogen diffusivity. Therefore, the
(2-1) charge transfer rate and hydrogen diffusivity must be high enough
to ensure a high charge/discharge rate, otherwise the charging or
discharging processes are retarded, and the electrochemical prop-
erties decrease for the anodes of the Ni-MH battery.
The Rct of alloy electrodes can be evaluated by electrochemical
impedance spectroscopy (EIS). Fig. 5 [30] is a typical EIS graph that
has a smaller semicircle, a larger semicircle and a straight line,
reflecting the contact impedance between the alloy particles and
the current collector, the charge-transfer resistance of the alloy
electrode and the Warburg impedance, respectively [31,32]. To
quantitatively analyze the Rct, an equivalent circuit, which can be
(2-2) seen in Fig. 5, is used to fit EIS data proposed by Kuriyama et al.
[31,32].
The exchange current density (I0) is used to characterize the
electrocatalytic activity of charge-transfer reactions on the inter-
face of the alloy electrodes [9]. The I0 can be obtained by measuring
the currents at different overpotentials (linear polarization). When
the overpotential changed within a small range, the I0 can be
calculated through the following equation [9]:
Id RT
I0 ¼ (2-4)
Fh
(2-3)
where R is the gas constant, T is the absolute temperature (K), Id is
the applied current density (mA/g) and h is the total overpotential
(mV). It can be found that RT/F is constant at a given temperature,
and there is a linear relationship between the current density and
the overpotential (Fig. 6 [30]). Therefore, the I0 can be obtained
according to Eqs. (2)e(4) by fitting a linear slope.
The hydrogen diffusion rate is a measure of how fast hydrogen
spontaneously diffuses into a material, which can be evaluated by D
(cm2/s), which is usually measured by potential-step methods.
According to the model of Zheng et al. [33], the D of hydrogen inside
the alloy particles can be estimated by fitting the slope of the linear
portion of the response curves using the following equation:
   2   
6FD p D
logi ¼ log ± 2 ðC0 dCs Þ d t (2-5)
da 2:303 a2
where i (A/g) is the diffusion current density, C0 (mol/cm3) is the
initial hydrogen concentration in the bulk of the alloy, Cs (mol/cm3)
is the hydrogen concentration on the surface of the alloy particles, a
(cm) is the alloy particle radius, d (g/cm3) is the density of the
hydrogen storage alloy and t (s) is the discharge time.
In summary, as negative electrode materials for Ni-MH power
batteries, hydrogen storage alloys must have high reversible
hydrogen storage capacities, sufficiently high electrochemical re-
action rates and high corrosion resistance in alkaline solution to
ensure excellent electrochemical performance.
168 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178

Table 2
The relationship of HRD to charge transfer rate and hydrogen diffusivity.

Samples Properties Rct I0 IL D or D/a2 HRD Ref.

La0.78Ce0.22Ni3.73Mn0.30Al0.17Co0.80 AB5-type ~0.6 U ~140 mA/g e D ¼ 0.207  1010 cm2/s HRD600 ¼ 43.47% [25]
La0.78Ce0.22Ni3.73Mn0.30Al0.17Fe0.80 ~2.1 U ~62 mA/g e D ¼ 0.186  1010 cm2/s HRD600 ¼ 54.73%
Ti12.5Zr21V10Cr8.5Mn2.6Co1.5Ni43.9 AB2-type e 25.5 mA/g e D ¼ 2.05  1010 cm2/s HRD50 ¼ 92.8% [26]
Ti12.5Zr21V10Cr8.5Mn23.6Co1.5Ni22.9 e 17.98 mA/g e D ¼ 1.54  1010 cm2/s HRD50 ¼ 83.9%
La0.7Mg0.3Ni2.65Mn0.1Co1.05 RE-Mg-Ni-based 35.4 mU 327.8 mA/g 1912.0 mA/g D ¼ 0.87  1010 cm2/s HRD1750 ¼ 61.4% [27]
La0.7Mg0.3Ni2.65Mn0.1Co1.15 44.9 mU 306.3 mA/g 1653.8 mA/g D ¼ 0.79  1010 cm2/s HRD1750 ¼ 50.2%
Ti0.8Zr0.2V2.7Mn0.5Cr0.8Ni0.75 V-based e 72.8 mA/g 501.9 mA/g D ¼ 0.257  1010 cm2/s HRD800 ¼ ~25% [28]
Ti0.8Zr0.2V2.7Mn0.5Cr0.8Ni1.25 e 85.6 mA/g 778.6 mA/g D ¼ 0.498  1010 cm2/s HRD800 ¼ ~70%
Mg50Co50 Mg-based 5.54 U 50.05 mA/g e D/a2 ¼ 2.048  105 cm2/s HRD400 ¼ 51% [29]
Mg50Co45Pd5 0.86 U 127.07 mA/g e D/a2 ¼ 3.623  105 cm2/s HRD400 ¼ 65%

3. Main hydrogen storage alloys for Ni-MH batteries
Hydrogen storage electrode alloys consist of two types of metal
elements in different stoichiometries, i.e., A and B elements with
positive and negative affinity to H, respectively. Depending on the
ratio of A to B, the hydrogen storage alloys can be principally
classified as AB5-type alloys, AB2-type alloys, A2B7-type or AB3-type
RE-Mg-Ni-based superlattice alloys. The performances of each type
of alloy differ greatly in terms of hydrogen storage capacity,
discharge capacity, activation and stability due to their different
compositions and structures. Some properties of these alloys are
shown in Table 3.
With a single CaCu5-type hexagonal structure, AB5-type
hydrogen storage alloys have a low electrochemical capacity. AB2-
type hydrogen storage alloys have higher electrochemical capacity
and the typical representative phases of AB2-type alloys are the
hexagonal C14 and cubic C15 Laves phases. However, binary AB2-
type compounds show poor electrochemical properties in alkaline
electrolytes due to the high stability of their hydrides. Optimizing
the C14/C15 phase abundance and forming third phases by multi-
elements and optimizing the composition can improve their per-
formances. RE-Mg-Ni-based hydrogen storage alloys, as novel
negative electrode materials for Ni-MH batteries, mainly contain
the LaNi5 and (La,Mg)Ni3 phases. In RE-Mg-Ni-based alloys, the
LaNi5 phase is not only a hydrogen-absorbing phase, but also acts as
a catalyst to activate the (La,Mg)Ni3 phase to absorb/desorb
hydrogen, and the (La,Mg)Ni3 phase could enhance the electrode
reaction kinetics, so that RE-Mg-Ni-based hydrogen storage alloys
show better electrochemical properties. For Ti-V-based alloys, both
the Ti-based C14-type Laves and V-based solid-solution phases
have high hydrogen storage capacity. The V-based solid-solution
phase shows poor electrochemical performance due to its stable
hydride, but the C14 Laves phase can work as a catalyst to catalyze
the V-based solid-solution phase to achieve reversible electro-
chemical hydrogen absorption/desorption. Mg-based hydrogen
storage alloys have very high hydrogen storage capacities of 7.6 and
3.6 wt% for MgH2 and Mg2NiH4, respectively. Nevertheless, crys-
talline Mg-based alloys show poor electrochemical properties at
room temperature, meaning that high temperatures are required
for dehydriding, in addition to their serious corrosion in alkaline
electrolytes. In this section, these alloys will be evaluated in detail,
and other novel and high energy density alloys, such as Co-based
alloys, are also discussed.
3.1. AB5-type hydrogen storage alloys
The typical representative of the AB5-type hydrogen storage
alloy is LaNi5. With a CaCu5-type hexagonal structure (space group
P6/mmmwith La (1a) in (0,0,0), Ni (2c) in (1/3,2/3,0) and Ni (3g) in
(1/2,0,1/2)), as shown in Fig. 7 [6,7], there are three octahedral sites
and three tetragonal sites, and H preferentially occupies the tetra-
hedral sites containing A2B2, AB3 and B4. One LaNi5 unit cell can
absorb six hydrogen atoms to form the LaNi5H6 hydride, which is
equivalent to a theoretical electrochemical capacity of 372 mAh/g.
Van Vucht et al. [34] first reported the LaNi5 alloy with reversible
hydrogen absorption/desorption properties in the late 1960s. In

Fig. 5. The electrochemical impedance spectra (EIS) of the La0.7Mg0.3Ni3.5alloy and

La0.7Mg0.3Ni3.5-Ti0.17Zr0.08V0.35Cr0.1Ni0.3 composite electrodes at 50% DOD and 303 K Fig. 6. Linear polarization curves (LP) of the La0.7Mg0.3Ni3.5alloy and La0.7Mg0.3Ni3.5-
[30]. Ti0.17Zr0.08V0.35Cr0.1Ni0.3composite electrodes at 50% DOD and 303 K [30].
 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178 169

Table 3
Typical characteristics of hydrogen storage alloys for Ni-MH battery application [4e15].

Types Compound Hydrides Hydrogen storage Discharge Advantages Disadvantages

(structure type) capacity (wt.%) capacity (mAh/g)

AB5 LaNi5 LaNi5H6 1.4 320 Resource-rich Low capacity

(Hexagonal)
AB2 TiMn2 TiMn2H2 1.7 440 High capacity Poor activation performance
(Hexagonal or cubic)
RE-Mg-Ni-based LaNi3 LaNi3H5 1.6 410 Good activation Poor cycle life
(Rhombohedral) performance
V-based VTi VTiH2 2.0 420 High capacity Poor activation
(C14-type Laves phase performance, high cost
and V-based solid-solution)
Mg-based Mg2Ni Mg2NiH4 3.6 500 Resource-rich, Poor stability
(Cubic) high capacity

Fig. 7. Crystal structure of LaNi5 alloy [6,7].

1973, Ewe et al. [35] reported the electrochemical performance of
the LaNi5 alloy; however, it showed poor cycling performance due
to pulverization and dissolution during the charge/discharge pro-
cess. Soon after, the COMSAT laboratory developed a Ni-MH battery
that used a LaNi5 alloy as a negative electrode, but the cycling life
still did not meet the practical application requirements. From then
on, great efforts have been made to improve the cycle life of LaNi5
alloys using alloy element substitution both for La and Ni. In 1984, a
breakthrough was accomplished for the life cycling of LaNi5
through partial substitution of Ni by Co [36]. This discovery acted as
the key for Ni-MH batteries to enter the market. Since then, sig-
nificant research has been completed to improve the overall per-
formances and reduce the cost of this type of alloy. In brief, the A
side (La) was substituted by mischmetal (cerium-rich mischmetal
(Mm) or lanthanum-rich mischmetal (Ml)) and the B side (Ni) was
partially substituted by Co, Mn, Al, Sn, Fe, Cr or Cu. The capacity of
AB5-type alloys are in the range of 250e350 mAh/g (Table 4)
[37e43]. Studies have shown that plateau pressures within the
range of 0.01e1 bar are suitable for the reversible electrochemical
reaction. Partial substitutions can obtain larger reversible electro-
chemical capacities and better kinetics than the LaNi5 parent
compound, which is attributed to the suitable plateau pressure. As
shown in Fig. 8 [7], the AB5 alloy with partial substitution of Mn, Al,
Co achieve suitable plateau pressure (0.01e1 bar), and
La0.62Ce0.27Pr0.03Nd0.08Ni3.55Co0.75Mn0.4Al0.3 is widely applied even
in today's Ni-MH batteries and has adequately met the

Table 4
Hydrogen capacity for various pseudo-binary AB5-type alloys [10].

Composition Csg (H/f.u), (PH2(bar)) Cel (mAh/g)

LaNi5 6.24, (25) 387

LaNi4.7Al0.3 5.85, (10) 370
LaNi4.25Co0.75 6.23, (10) 386
LaNi3Co2 5.39, (10) 334
LaNi4Cu 5.45, (10) 334
LaNi4Fe 5.24, (10) 327
LaNi4.6Mn0.4 6.21, (10) 386
LaNi4Mn 5.82, (10) 364
LaNi4.5Sn0.5 5.25, (10) 304
LaNi3.55Mn0.4Al0.3Co0.75 5.60, (10) 334
Fig. 8. Linear dependence of the plateau pressure as a function of the intermetallic cell
MmNi3.55Co0.75Mn0.4Al0.3 5.30, (10) 332
volume for various La1yRyNi5-xMx compounds at room temperature [7].
170 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178
requirements for a practical battery [44].
Unfortunately, the cost of the raw materials in this alloy is high
as they contain Co, Pr and Nd, even though their contents are at low
levels. Cobalt, the key element to maintain long life in the com-
mercial hydrogen storage alloy mentioned above, accounts for
about 40e50% of the total cost of this typical alloy. Although Pr and
Nd can improve the activation properties of hydrogen storage alloys
and increase their high-rate dischargeability and cyclic stability, the
price of Pr and Nd are about 5e10 times of that of La-Ce. Therefore,
it is important to reduce the content of high cost Co, Pr and Nd to
increase the market competitiveness of Ni-MH batteries. As a
result, significant work has been concentrated on developing high
performance, Co/Pr/Nd-free or low-Co/Pr/Nd hydrogen storage al-
loys [45e49]. For instance, Wei et al. [45] reported that the low-Co,
Pr/Nd-free La0.9Li0.1Ni3.2Co0.3Al0.3 alloy has a maximum discharge
capacity of 328 mAh/g and retained 71.5% after 230 charge/
discharge cycles. Balogun et al. [47] investigated the electro-
chemical properties of a series of La-Ni-Co-Mn-Al alloys and noted
that the LaNi4.2Co0.3Mn0.3Al0.2 alloy has a maximum discharge ca-
pacity of 330.4 mAh/g and showed a good cycle life. The Pr/Nd-free
La9.5Ce6.4Ni69Co4.7Mn4.3Al5.7Zr0.1Si0.3 alloy prepared by induction
melting has a maximum discharge capacity of about 340 mAh/g,
the same as the commercial AB5 alloy containing Pr and Nd [49].
Another challenge is the poor high-rate dischargeability of
hydrogen storage electrode materials for the applications of Ni-MH
batteries in high-power fields. Numerous efforts have been
implemented to improve the electrochemical performance of AB5-
type alloys, such as annealing treatment, surface treatment, addi-
tives and non-stoichiometry [50e54]. Shen et al. [55] studied the
surface modification of an AB5-type alloy (La0.64Ce0.25Pr0.03Nd0.08-
Ni4.19Mn0.31Co0.42Al0.23) electrode with polyaniline by electroless
deposition. The result revealed that through the polyaniline-
coating, the high-rate discharge ability increased from 8.5 to
45.0% at a discharge current density of 1440 mA/g. Li et al. [56]
reported the synthesis of a composite by coating hydrogen stor-
age alloys (HSAs) with reduced graphite oxide via a top-down
route. The high-rate dischargeability was distinctly enhanced
with the capacity retention rate reaching 51.3% at a discharge cur-
rent density of 3000 mA/g, which is almost four times that of the
bare HSA electrode (13.5%). Recently, Zhou et al. [57] indicated that
after hot-alkali treatment and duplex hot-alkali treatments with
reducing agents, the MmNi3.7Co0.7Mn0.3Al0.3 alloy shows excellent
high-rate output performance, even at low temperature.
So far, commercial AB5-type hydrogen storage alloys have ach-
ieved a reversible capacity of ~320e350 mAh/g. Obviously, the
electrochemical capacity of AB5-type hydrogen storage alloys has
small space for improvement, which is an unfortunate situation
that is attributed to their structure. Therefore, novel electrode al-
loys with higher hydrogen storage densities need to be developed
to match the requirements of increasing energy density in Ni-MH
batteries.
3.2. AB2-type alloys
AB2-type alloys are considered as second-generation electrode
alloys for Ni-MH batteries due to their higher energy densities and
the earliest investigations were based on binary compounds with
A ¼ Zr or Ti and B ¼ V, Cr or Mn. The Laves phases, mainly the
hexagonal C14 phase (MgZn2), the cubic C15 phase (MgCu2) and the
hexagonal C36 phase (MgNi2), are typical representatives of AB2-
type intermetallic compounds, corresponding to a compact stack-
ing for an atomic ratio of RA/RB ¼ 1.225 [58,59]. Both the C14 phases,
such as ZrMn2 and TiMn2, and C15 phases, such as ZrV2, are good
hydrogen absorbers, while the C36 phase is a poor hydrogen
absorber and is therefore not discussed here. There are the same
number of interstitial tetrahedral sites for hydrogen occupation in
the C14 or C15 structures with environments A2B2, AB3 and B4
(Fig. 9) [6]. The A2B2 sites are the most occupied sites owing to their
high coordination with A-type elements and they show the stron-
gest affinity to hydrogen.
Owing to the high stability of their hydrides, binary AB2-type
compounds show poor electrochemical properties in alkaline
electrolytes. However, interest soon turned to multi-element
pseudo binary intermetallics and modifying the A/B stoichiom-
etry. The basic multi-element AB2-type alloys mostly contain Ti, Zr,
V, Ni. Cr, Co, Al and Fe. Ti, Zr and V are the hydride forming ele-
ments, Co and Mn provide the surface activity, and Cr, Al and Fe
increase the corrosion resistance. It should be emphasized that Ni is
the key element in all Ni-MH battery materials, including AB5, AB3-
3.5, AB2 and AB. In the case of AB2 compounds, adding Ni can
improve the catalytic activity of the redox reaction. The discharge
capacity of the multi-element AB2-type alloys ranges from 370 to
450 mAh/g, which is much higher than that of AB5-type alloys, but
with slow activation and poor cycle life. These drawbacks are
caused by surface passivation, in which a very dense layer of metal
oxides forms on the surface during the charge/discharge cycling
process, which blocks the electrochemical reaction and hydrogen
diffusion, and increases electrical resistance.
To improve the overall electrochemical properties of AB2-type
alloys, more work has been concentrated on the optimization of the
composition. The alloy Zr0.8Ti0.2Mn0.8V0.2Ni0.8C0.15Al0.05, with the
C14 structure, exhibited a reversible electrochemical capacity of
380 mAh/g after activation [60]. The ZrMn0.5Cr0.2V0.1Ni1.2, with the
C15 structure, also deliver a capacity of 380 mAh/g, and has been
established as a reference compound [61]. As an anode material
developed by the Ovonic battery company, the V5Ti9Zr26.2-
Ni38Cr3.5Co1.5Mn15.6Al0.4Sn0.8 alloy provides an energy density of
1057 W/kg with an excellent stability within 1000 cycles [62e64].
Further studies have found that the formation of ZrNi and TiNi
phases played important roles in improving the overall electro-
chemical performances of AB2-type compounds [65,66]. Opti-
mizing the C14/C15 phase abundance can also improve their
activation, capacity retention rates and high-rate dischargeability.
However, a clear relationship between crystal structure and
electrochemical properties has not yet been established. Moreover,
composites with other types of alloys to introduce some catalytic
structures is an effective way to improve the performance of AB2-
type compounds. For instance, for a Ti0.9Zr0.2Mn1.5Cr0.3V0.3 (AB2)
composite with LaNi3.8Mn0.3Al0.4Co0.5 (AB5) formed by ball milling,
the maximum discharge capacity increases from 48.6 to 310.4 mAh/
g, and that of a Ti0.9Zr0.2Mn1.5Cr0.3V0.3-La0.7Mg0.25Zr0.05Ni2.975-
Co0.525 (AB3.5) composite reaches 314.0 mAh/g [67]. Compared to
the AB5-type hydrogen storage alloys, the AB2-type compounds still
Fig. 9. Crystal structures of C14 (a) and C15 (b) Laves phases and their possible
interstitial sites for hydrogen occupancy [6].
 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178
show slower activation and lower rate capabilities. AB2-type com-
pounds with higher energy densities, higher rate capabilities, faster
activation and lower cost are still desired for Ni-MH batteries.
3.3. A2B7-type and AB3-type RE-Mg-Ni-based superlattice alloys
Some binary La-Ni alloys, such as LaNi (AB-type), LaNi2 (AB2-
type), LaNi3 (AB3-type) and La2Ni7 (A2B7-type), have higher theo-
retical electrochemical capacities than the LaNi5 alloy, but the high
stability of their hydrides restricts their development. In 1997, Kadir
et al. [68] reported a series of new ternary RMg2Ni9 alloys (where
R ¼ La, Ce, Pr, Nd, Sm or Gd) prepared by sintering. Later studies
[69e80] found that RE-Mg-Ni-based alloys contained the
(La,Mg)2Ni7 phase with a rhombohedral PuNi3-type structure or
the (La,Mg)2Ni7 phase with a hexagonal Ce2Ni7-type structure.
Fig. 10 shows that their structure can be considered as the stacking
of AB5 units (CaCu5-type structure) and AB2 units (MgCu2 structure)
along the c-axis direction with ratios of n:1 [74]. In addition, many
studies have shown that all the AB2C9-type alloys (A ¼ RE or Ca, B ¼
Mg or Ca, C ¼ Ni) have the same structure as LaMg2Ni9 alloys, so
they can be also labeled as AB2C9-type or AB3-type structures
[69e80].
In 2000, Chen et al. [72] evaluated LaCaMgNi9, CaTiMgNi9,
LaCaMgNiAl3 and LaCaMgNiMn3 alloys and all of them showed
good activation performance. The maximum discharge capacity of
LaCaMgNi9 reached 356 mAh/g, which is higher than that of AB5-
type alloys, but they exhibit poor cyclability and low high-rate
dischargeability. Around the same time, Kohno et al. [73] re-
ported that the La0.7Mg0.3Ni2.8Co0.5 alloy has a maximum discharge
capacity of 410 mAh/g, which is much higher than that of com-
mercial Ni-MH batteries. Zhang et al. [81] investigated the structure
Fig. 10. Crystal structure of AB3-type alloys. (a) Interrelation of stacking layers, (b)
some of the interstitial sites [74].
171
and electrochemical properties of La0.7Mh0.3Ni2.975-xCo0.525Mnx
(x ¼ 0, 0.1, 0.2, 0.3, 0.4) alloys and found that all these alloys are
mainly composed of the La(La,Mg)2Ni9 phase with the rhombohe-
dral PuNi3-type structure and the LaNi5 phase with the CaCu5-type
structure. The alloys have a maximum discharge capacity of
330e360 mAh/g and excellent high-rate dischargeability but poor
cycle life. A La1.5Mg0.5Ni7 alloy has a double-phase structure with
the Gd2Co7-type and Ce2Ni7-type phases, and its electrochemical
capacity could be up to 390 mAh/g, as reported also by Zhang et al.
[82]. Thus, both A2B7-type and AB3-type RE-Mg-Ni-based hydrogen
storage alloys are attracting more and more attention as negative
electrode materials for Ni-MH batteries.
Significant efforts have been made to improve the electro-
chemical properties of RE-Mg-Ni-based hydrogen storage alloys.
Liao et al. [75,76] studied the ternary LaxMg3-xNi9 (x ¼ 1.0e2.2)
alloys and found that the discharge capacities and cycle lives of
LaxMg3-xNi9 alloys show an increasing trend with increasing Mg
content. In particular, La2MgNi9 has a maximum discharge capacity
of 397.5 mAh/g and HRD1200 ¼ 52.7%, exhibiting good overall
electrochemical performance. Guo et al. [77] obtained the same
conclusion. Pan et al. [78] investigated the electrochemical prop-
erties of a series of La0.7Mg0.3(Ni0.85Co0.15)x (x ¼ 2.5e5.0) alloys and
found that this type of alloy showed high discharge capacities,
outstanding high-rate dischargeability and good kinetics, but poor
capacity retention rates (Fig. 11(a)). Based on the aforementioned
studies, Liu et al. [79] formulated the La0.7Mg0.3Ni3.4-xCoxMn0.1
(x ¼ 0e1.6) alloys and suggested that the capacity retention rate of
alloy electrodes increases with increasing Co content (Fig. 11(b)).
The alloy achieved the best electrochemical properties at x ¼ 0.75.
Later [80], they partially substituted Ni with Al to obtain a series of
La0.7Mg0.3Ni2.65-xCo0.75Alx (x ¼ 0e0.5) alloys and found that the
discharge capacity and high-rate dischargeability only marginally
decrease, but the capacity retention rate improved distinctly from
32.0% (x ¼ 0) to 73.8% (x ¼ 0.3) after 100 charge/discharge cycles
(Fig. 11(c)). Further studies suggested that there is a dense Al2O3
layer formed on the alloy surface during the cycling process, which
improves the capacity retention rate by restricting pulverization
and dissolution of the active materials [80]. In order to reduce the
alloy's cost, Tang et al. [83] substituted La with a Ml and studied the
electrochemical properties of a Ml0.7Mg0.2Ni2.8Co0.6 alloy. As a
result, this alloy is mainly composed of the CaCu5 and PuNi3 phases
and has a capacity of 380 mAh/g and excellent cycle stability,
exhibiting good overall electrochemical performance.
Research has been ongoing to further improve the overall
electrochemical performance of RE-Mg-Ni-based alloys and Table 5
lists part of the alloys developed so far. Yang et al. [97] investigated
the surface coating of La0.88Mg0.12Ni2.95Mn0.10Co0.55Al0.10 alloy
powder with Ni-Cu-P by an electroless composite plating treat-
ment. The discharge capacity, cycle life and high-rate discharge-
ability were all noticeably improved by this treatment. Similarly,
polyaniline electroless-deposition was applied to a La0.80Mg0.20-
Ni2.70Mn0.10Co0.55Al0.10 hydrogen storage alloy powder to improve
electrochemical and kinetic properties [98]. Owing to the poly-
aniline coating, both the capacity retention rate and high-rate
dischargeability were increased. The present author [99] added
graphene to the AB3-type R-Mg-Ni-based alloy by a plasma milling
method, finding that both the discharge capacity and high-rate
dischargeability were significantly improved, and it is worth
mentioning that the HRD1750 was increased from 53.7% to 89.6%.
This is important for using this type of alloy electrode in power
batteries. In order to further decrease the cost of the alloy, Cao
et al. [100] prepared a high-Sm, Pr/Nd-free and low-Co
La0.95Sm0.66Mg0.40Ni6.25Al0.42Co0.32 alloy by an induction melting.
The alloy shows high discharge capacity and excellent cyclic
properties with the maximum discharge capacity reaching
172 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178
Fig. 11. Cyclic stability of different alloys. (a) forLa0.7Mg0.3(Ni0.85Co0.15)x (x ¼ 2.5e5.0)
alloys, (b) for La0.7Mg0.3Ni3.4-xCoxMn0.1 (x ¼ 0e1.6) alloys and (c) for La0.7Mg0.3Ni2.65-
xCo0.75Alx (x ¼ 0e0.5) alloys [78e80].
338.0 mAh/g and 80% of the capacity being retained after 239 cycles
at 1C.
More recently, Yan et al. [95] studied new La-Y-Ni system alloys
prepared by the induction-melting rapid-quenching method. The
A2B7-type LaY2Ni9.7Mn0.5Al0.3 alloy has a maximum discharge ca-
pacity of 385.7 mAh/g and a 76.6% capacity retention rate after 300
cycles, which has a higher discharge capacity and better cycle sta-
bility than the AB5-type alloy. Liu et al. [96] reported that the
La0.78Mg0.22Ni3.73 alloy prepared by step-wise annealing the as-cast
alloy sample has a maximum discharge capacity of 372 mAh/g and
achieves a cycle life of above 400 cycles (the discharge capacity
decreases to 60% of the maximum discharge capacity), and the alloy
exhibits an excellent kinetic performance with a high-rate dis-
chargeability of 62.4% at 1500 mA/g.
Nowadays, RE-Mg-Ni-based alloys have already been used as
commercial negative electrode materials in Ni-MH batteries, but
new types of RE-Mg-Ni-based alloys with higher electrochemical
capacities and longer cycle lives still need to be developed to meet
the increasing energy demands.
3.4. Ti-V-based alloys
As a result of their higher hydrogen storage capacities, both Ti-
based C14-type Laves phase and V-based solid-solution type alloys
have attracted extensive attention. Generally, V-based solid-
solution phase alloys have high hydrogen absorption capacities,
but their reversible hydrogen absorption/desorption capacity is low
due to the formation of stable VH, and they do not have high
reversible electrochemical discharge capacity due to poor electro-
catalytic activity in alkaline electrolytes [101,102]. The Ti-based C14
type Laves phase has a high electro-catalytic activity [101,102] and
it can catalyze the V-based solid-solution phase to achieve
reversible electrochemical hydrogen absorption/desorption. Of
course, the Ti-based C14 type Laves phase itself has a high elec-
trochemical hydrogen storage capacity. Thus, Ti-V-based alloys
have the synergistic effect of Ti-based alloys with V-based alloys
and exhibit high electrochemical properties.
Tsukahara et al. [103] reported that the V3TiNi0.56 alloy has a
capacity of 420 mAh/g, but with a very poor cycle life, with the
discharge capacity decreasing to 0 mAh/g after 77 cycles. They
noted that forming a second phase, such as the C14 Laves or TiNi
phases, could catalyze the V-based solid-solution phase to absorb
and desorb a large amount of hydrogen, and the loss of reversibility
maybe due to the disappearance of the secondary phase during the
charge/discharge cycling process [103,104]. Thus, it is believed that
creating multiphase alloys is a feasible approach to improve the
electrochemical properties of Ti-V-based hydrogen storage alloys.
Following this idea, Pan et al. [105] and Zhu et al. [106] studied the
electrochemical properties of Ti-V-based alloys with partial sub-
stitution by a series of metal elements, such as Zr, Fe, Ni, Cr, Mn and
Pd. The Ti1-xZrxV1.6Mn0.32Cr0.48Ni0.6 (x ¼ 0.2e0.5) alloys mainly
consist of the hexagonal structured C14 type Laves phase and the
body centered cubic structured V-based solid-solution phase [106].
After partial substitution of Ti by Zr, the capacity retention rate
significantly improved but the activation, maximum discharge ca-
pacity and high-rate dischargeability decreased. By partial substi-
tution of V with Fe, a Ti0.8Zr0.2V2.7-xMn0.5Cr0.8Ni1.0Fex (x ¼ 0e0.5)
alloy was created, and both the cyclic stability and high-rate dis-
chargeability were improved [107]. In addition, the cost of the alloy
was deceased as pure vanadium is very expensive. They further
studied a series of superstoichiometric Ti0.8Zr0.2(V0.533Mn0.107-
Cr0.16Ni0.2)x (x ¼ 2e6) alloys containing a C14 Laves phase and a V-
based solid solution phase, and demonstrated that the Ti0.8Zr0.2-
(V0.533Mn0.107Cr0.16Ni0.2)5 alloy has a maximum discharge capacity
of 380 mAh/g [105]. Here again, the V-based solution phase is the
major hydrogen absorbing phase and the C14 Laves phase acts not
only as a hydrogen absorbing phase, but also as a catalyst for the
electrochemical hydrogenation and dehydrogenation of the V-
based phase [108]. Recently, Wang et al. [109] reported that the
cycling stability of a Ti0.10Zr0.15V0.35Cr0.10Ni0.30 alloy was distinctly
improved after compositing with LaNi5.
Some properties of Ti-V-based alloys are listed in Table 6. By
summarizing the obtained results, we can obtain the following
principle for Ti-V-based alloys. As essential elements of Ti-V-based
alloys, Ti, Zr and V are the primary hydrogen absorption elements,
 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178 173

Table 5
Electrochemical properties of various ReMgeNi-based alloy electrodes.

Alloy Maximum discharge capacity (mAh/g) High-rate dischargeability Capacity retention Ref.

La0.7Mg0.3Ni2.8Co0.5 410 e e [73]

La0.7Mg0.3(Ni0.85Co0.15)3.5 395.6 HRD1000 ¼ 85.8% S60 ¼ 45.9% [78]
La2MgNi9 397.5 HRD1200 ¼ 52.7% S100 ¼ 60.6% [76]
La0.7Mg0.3Ni3.5 352.8 HRD800 ¼ 79.4% S100 ¼ 58.4% [84]
La0.7Mg0.3Ni2.9(Al0.5Mo0.5)0.6 397.6 HRD1200 ¼ 70.5% S70 ¼ 70.8% [85]
La0.4Nd0.4Mg0.2Ni3.2Co0.2Al0.2 372 HRD1200 ¼ 39.2% S100 ¼ 82.3% [86]
La0.6Pr0.1Mg0.3Ni2.45Co0.75Mn0.1 372.7 HRD1000 ¼ 70.1% S100 ¼ 78.4% [87]
La1.8Ti0.2MgNi8.7Al0.3 339.6 HRD1400 ¼ 61.1% S205 ¼ 60% [88]
La0.75Mg0.25Ni3.5 349 HRD1500 ¼ 41.5% S100 ¼ 82.8% [89]
La0.4Pr0.4Mg0.2Ni3.15Co0.2Al0.1Si0.05 377.5 e S100 ¼ 95.72% [90]
Pr2MgNi9 342 HRD1500 ¼ 56.7% S100 ¼ 86.3% [91]
Nd2MgNi9 341 HRD1500 ¼ 58.7% S100 ¼ 84.5% [91]
La4MgNi19 367 HRD1500 ¼ 66.4% S100 ¼ 85.7% [92]
La0.6Gd0.2Mg0.2Ni3.05Co0.25Al0.1Mn0.1 391.2 HRD900 ¼ 75.3% S100 ¼ 89.8% [93]
La0.75Mg0.25Ni3.05Co0.20Al0.10Mo0.15 372 HRD1500 ¼ 60.1% S100 ¼ 80.9% [94]
LaY2Ni9.7Mn0.5Al0.3 385.7 e S300 ¼ 76.6% [95]
La0.78Mg0.22Ni3.73 372 HRD1500 ¼ 62.4% S100 ¼ 85.3% [96]

Table 6
Electrochemical properties of some Ti-V-based alloy electrodes.

Alloy Maximum discharge capacity (mAh/g) High-rate dischargeability Capacity retention Ref.

Ti0.8Zr0.2V2.7Mn0.5Cr0.8Ni1.25 328.6 e S200 ¼ 73.13% [28]

Ti0.17Zr0.08V0.34Pd0.01Cr0.1Ni0.3 317 e S100 ¼ 86% [110]
Ti0.17Zr0.08V0.35Cr0.1Ni0.25Mn0.05 374.1 e S600 ¼ 62.9% [111]
Ti0.8Zr0.2V2.7Mn0.5Cr0.6Ni1.15Co0.1Fe0.2 333.4 HRD600 ¼ 62.5% S200 ¼ 79.8% [112]
Ti0.7Y0.1Zr0.2V2.7Mn0.5Cr0.6Ni1.25Fe0.2 360.2 HRD600 ¼ 67.9% S200 ¼ 69.8% [113]
Ti0.17Zr0.08V0.35Cr0.1Ni0.3B0.1 329.0 HRD800 ¼ 72.5% S200 ¼ 89.4% [17]
Ti0.26Zr0.07V0.235Mn0$1Ni0.33Gd0.005 421 e S30 ¼ 41.07% [114]

Ni provides the catalytic activity for the redox reaction, Co and Mn
improve surface activity and Cr, Fe and Al increase the anti-
corrosion ability. Optimizing the processing of an alloy, e.g., rapid
solidification, can refine the microstructure and improve the uni-
formity, and thus prevent pulverization of the alloy particles and
improve the anti-corrosion ability [115,116]. However, the cyclic
stability and the high-rate dischargeability are still not satisfactory
for practical application, although the Ti-V-based alloys have been
extensively investigated and their overall electrochemical perfor-
mances have been markedly improved. Further studies are still
required and composition optimization, annealing treatment and
composites with other types of alloys are effective ways to improve
the overall electrochemical properties of Ti-V-based alloys.
hexanolmicroemulsion has a maximum discharge capacity of
357 mAh/g and this is still maintained after 50 discharge cycles.
Using a vacuum freeze-drying method, the as-prepared Co-B alloy
has a maximum discharge capacity of 438 mAh/g [120]. In a recent
study, an amorphous Co-B alloy prepared by the reduction of CoSO4
by KBH4 has an extremely high discharge capacity of 968.6 mAh/g
and the introduction of NaS2O3 into the alkaline electrolyte is
helpful for storing the battery for long durations (Fig. 12) [121].
Additionally, in a 6 M KOHþ0.09 M ethylenediamine electrolyte,

3.5. Co-based alloys

Although the electrochemical properties of hydrogen storage

alloy anode materials for Ni-MH batteries have improved after vast
research, their capacity is relatively low in comparison with, in
particular, Li-ion batteries. Recently, Co-based alloys, especially CoB
alloys, were found to have relatively high discharge capacities,
excellent cycle lives and extremely high catalytic activities when
used as negative electrodes in an aqueous KOH electrolyte. Wang
and coworkers [117] demonstrated that ultra-fine particles of the
Co-B amorphous alloy could be successfully prepared through the
reduction of Co(SO4)2 by NaBH4. As an anode material in an alkaline
rechargeable battery, the discharge capacity of Co-B is more than
600 mAh/g for the initial cycle. In addition, the cycling ability and
high rate capability are fairly good. Liu et al. [118] found that the
capacity retention of CoxB (x ¼ 1, 2 and 3) alloys prepared by a Fig. 12. (a) CV curves of the Co2.012BHy sample, (b) Discharge curves of the Co2.012BHy
sample at different cycles at 60 mA/g, (c) XRD patterns of the CoOOH precipitate
magnetic levitation melting method was more than 93% after 100 (insert: SEM image of the precipitate), and (d) Cycling stability of the Co2.012BHy
charge/discharge cycles. Co-B prepared by Tong et al. [119] in a sample in the alkaline electrolyte with different additions of Na2S2O3 at a charge and
water/cetyl-trimethyl-ammonium bromide/n- discharge current density of 150 mA/g [121].
174 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178
the CoB alloy prepared from the precursor of CoCl2$6H2O exhibits a
high discharge capacity and a long cycle life at an elevated tem-
perature of 55  C, i.e., the discharge capacity is still up to 601.7 mAh/
g after 100 discharge cycles [122]. Other Co-based alloys, including
Co-P, Co-Si, Co-BN and Co-Si3N4, also show high discharge capac-
ities. For instance, the Co-BN alloy prepared by ball milling has a
maximum discharge capacity of 450 mAh/g, which remains at
280 mAh/g after 50 charge/discharge cycles [123]. By the same
preparation method, the Co-Si3N4 alloy shows equivalent electro-
chemical performances [124].
However, there are two different viewpoints on the principles of
the electrochemical reaction of Co-based alloys used as electrode
materials in batteries. Mitov et al. [125] studied the Co-B nano-alloy
prepared by a chemical reduction method via cyclic voltammetry
(CV) testing and found that the CV curve of this alloy is similar to
that of hydrogen storage electrode alloys. Thus, they judged that
the principles of the electrochemical reaction of Co-B alloys were
based on hydriding/dehydriding. Wang et al. [117] agreed with this
view after carrying out a similar investigation. Later on, Liu et al.
[126] studied two types of Co-B alloys prepared by high tempera-
ture solid state reaction and an arc melting method, respectively,
they considered that boron plays a role for hydrogen absorbing and
the electrode reaction is given by:
Charge
 * Co2 BH þ OH 
Co2 B þ H2 O þ e )
Discharge
He et al. [127,128] and Cao et al. [129] investigated the electro-
chemical properties of Co-Si and Co-P alloys, respectively, and they
all approved the hydriding/dehydriding principle. They reported
that the reactions proceed as follows:
Charge
* CoSiH þ OH
CoSi þ H2 O þ e )
Discharge
Charge
CoP þ H2 O þ e ) * CoPH þ OH
Discharge
In those studies, the researchers who supported the electro-
chemical hydrogen storage mechanism generally believed that the
non-metallic elements P, Si and B in the Co-based alloys play an
important role in hydrogen absorbing. But there are also a few
studies that deem that Co can absorb and release hydrogen at room
temperature, because the measured capacity is actually equivalent
to the electrochemical hydrogen storage of Co. Chung et al.
[130,131] compared the X-ray diffraction (XRD) patterns of a Co
electrode before and after charging, finding that the structure of Co
transformed from a stable HCP phase to an unstable FCC phase.
Thus, they concluded that the charge/discharge process occurred in
the Co electrode via the following reaction:
Charge
Co þ cH2 O þ ce ) * CoHc þ cOH
Discharge
Another viewpoint is the same as for the Fe, Cd and Zn elec-
trodes, belonging to the dissolution-precipitation mechanism. Liu
et al. [118] used scanning electron microscopy (SEM), X-ray
photoelectron spectroscopy (XPS) and XRD to investigate a series of
Co-B alloys before and after chargeedischarge, finding that both Co
and B were oxidized in the process of discharging, but only Co can
be reduced, the oxidation of B is irreversible, and the oxidation
products of B is gradually eluted into the electrolyte during the
chargeedischarge cycling process. This point has also been
confirmed by other studies [132e134]. They favor the reaction
occurring in the bulk of the Co-B alloy electrode at the beginning of
the discharge process as follows:
CoBc þ OH  e /CoðOHÞ2 þ BO3 3 þ H2 O (3-5)
After B is oxidized completely, the later chargeedischarge pro-
cess is the same as that of a Cd electrode:
Charge
CoðOHÞ2 þ e ) * Co þ OH (3-6)
Discharge
Wherein B plays an important role for the electrochemical
properties of the Co-B alloy: (1) at the beginning of the discharge
process, B is oxidized to BO33 , which will increase the discharge
capacity of the alloy electrode. (2) BO3
3 , the oxidation product of B,
is continuously dissolved in the electrolyte, so that the new surface
of Co is exposed, reducing the passivation of Co, which will increase
the discharge capacity and high-rate dischargeability. This means
that B plays the role of an activator in the Co-B alloy. Lu et al. [123]
and Yao et al. [124] also support the dissolutioneprecipitation
mechanism after investigating the electrochemical properties of
the Co-BN and Co-Si3N4 alloys, respectively. Obviously, further
research is necessary to clarify this argument.
3.6. Mg-based alloys
(3-1) High-energy density, long endurance and excellent rate per-
formance are the standards of ideal electric vehicles, as determined
by the performance of the onboard battery. As stated previously,
the progress of industries advances rapidly, traditional energy
sources are dwindling and environment concerns are increasing,
therefore, the development of an ideal battery with a high capacity,
long life, outstanding high charge/discharge rate, environmentally
friendliness, safety and low cost for electric vehicles to ease these
(3-2)
problems is imperative. Mg-based hydrogen storage alloys have a
very high hydrogen storage capacity, with 7.6 and 3.6 wt% for MgH2
and Mg2NiH4, respectively, corresponding to theoretical capacities
(3-3) of ~2200 and 999 mAh/g, respectively [135e137]. This is much
higher than that of AB5, AB3, AB2 and Ti-V-based hydrogen storage
alloys. In addition, Mg is an abundant and cheap element. There-
fore, Mg-Ni based alloys were regarded as very promising candi-
dates as hydrogen storage alloys for Ni-MH batteries. Originally,
Mg-based alloys showed poor electrochemical properties due to
their poor hydriding/dehydriding kinetics at room temperatures.
By 1986, Sapru et al. [138] prepared the Mg52Ni48 amorphous alloy
using a sputtering method and the maximum discharge capacity of
the alloy was 500 mAh/g at the discharge current density of 50 mA/
g. Lei et al. [139] reported that the Mg50Ni50 amorphous alloy
prepared by ball milling showed good catalytic activity at room
temperature and the first discharge capacity can reach 500 mAh/g.
Iwakura et al. and Nohara et al. [140,141] further increased the
discharge capacity of Mg50Ni50 to higher than 1000 mAh/g. Lee
et al. [142] noted that the surface energy of the amorphous or
(3-4) nanocrystalline electrode is higher than the crystalline one, and the
hydrogen diffusion and charge transfer reaction is enhanced. Since
then, amorphization and nanocrystallization have been regarded as
very effective ways for activating Mg-based alloy electrodes.
To further improve the electrochemical properties of Mg-based
alloys, alloying with other elements was attempted. Notten et al.
[143,144] investigated the electrochemical properties of Mg-X
(X ¼ Sc, Ti, V and Cr) binary alloys. They exhibited superior high
reversible capacity ranges from 1300 to 1800 mAh/g, five times
higher than commercial AB5-type materials. Tian et al. [145,146]
reported a series of Mg0.9-xTi0.1PdxNi (x ¼ 0.04, 0.06, 0.08, 0.10)
alloys for electrode materials. Among them, Mg0.9Ti0.1Ni1-xPdx
(x ¼ 0, 0.5, 0.10, 0.15) amorphous alloys showed good cycling
 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178
stability, in which a Mg0.8Ti0.1Pd0.1Ni alloy maintained a discharge
capacity of 200 mAh/g after 80 charge/discharge cycles. By adopt-
ing special preparation methods, Mg-based alloys have been ob-
tained with unique structures. For example, a quaternary
nanocrystalline Mg1.95Y0.05Ni0.92Al0.08, which was prepared by
sintering followed by ball milling with Ni powder, showed an
excellent cycling life that maintained nearly 96% of the initial ca-
pacity retention rate of 385 mAh/g after 140 cycles (Fig. 13) [147].
Mixing Mg-based alloys with some other hydrogen storage alloys
or compounds with high catalytic activity or good anti-corrosion
capability is another strategy to improve the performance of Mg-
based anodes. A significant number of studies have focused on
the effect of the addition of AB5-type alloys and the results show
that the hydrogen storage performances of Mg-based alloys
improve distinctively after alloying with AB5-type alloys
[148e150]. For example, when MgH2 is ball milled with commer-
cial MmNi5 powders, the composites show faster hydriding/dehy-
driding kinetics, especially at low temperature hydrogenation, than
the original MgH2 [148]. Mg-Ni-based alloys introduced with car-
bon by a mechanical alloying method showed a discharge capacity
of 415 mAh/g at the first cycle and it only dropped by 5.3% in the
second cycle [151]. Recently, Huang et al. [152] reported that the
electrode of MgNi-10 wt% TiNi0.56Co nanocomposition has a
maximum discharge capacity of 397 mAh/g with a capacity reten-
tion rate of 62% (S50). Although progress has been achieved, the
cyclability of Mg-Ni-based anodes is still unfortunately poor due to
rapid dissolution of magnesium in alkaline solution [153,154].
Therefore, the practical application of Mg-based alloys is not yet
possible.
Recently, a series of new Mg-M (M ¼ Ni, La, Nd, Ag, Y and
mischmetal)-based hydrogen storage alloys have been developed
via different methods and they show fast kinetics and reasonably
high capacity [155e161]. In addition, Mg-based amorphous alloys
have also been developed with a high hydrogen storage capacity.
This provides new possibilities for developing negative electrode
alloys. Nevertheless, it is still a great challenge to develop Mg-based
alloys as negative electrodes for Ni-MH batteries.
Fig. 13. Capacity decay of the composite magnesium alloy electrodes with different
crystalline sizes [147].
175
4. Summary
Developing clean and fuel-efficient HEVs, electric vehicles and
distributed energy storage stations are appropriate approaches to
realize a green energy society. Ni-MH rechargeable batteries are
preferred for portable power tools and HEVs, owing to their
comparatively high-energy density and good environmental
compatibility. As anode materials for Ni-MH batteries, hydrogen
storage alloys have been extensively studied in the past several
decades.
In this review, we have primarily presented the development of
hydrogen storage alloys with the focus on Ni-MH power batteries.
The principles of Ni-MH batteries, electrochemical hydrogen stor-
age thermodynamics and electrochemical hydrogen storage ki-
netics have been discussed at first, and then, the relationships
between alloy compositions, crystal structures, microstructures
and electrochemical properties have also been evaluated. In
particular, the recent advance in hydrogen storage electrode alloys
have been summarized with the emphasis on AB5- and AB2-type
alloys. The AB5-type alloys with a typical composition of
MmNi3.55Co0.75Mn0.4Al0.3 (Mm ¼ La0.62Ce0.27Pr0.03Nd0.08) are most
popular and marketable electrode alloys used for Ni-MH batteries.
However, these alloys have small room to grow due to their low
theoretical electrochemical capacity of 372 mAh/g. Although AB2-
type alloys have a higher capacity, they have relatively poor cyclic
stability and are costly to produce. An effective way to improve
their performances is to combine AB5 and AB2 units to get alloys
with AB3- or A2B7-typed structures. In addition, more Mg is added
into alloys. This has led to the development and commercialization
ofAB3- or A2B7-type RE-Mg-Ni-based alloys as negative electrode
materials in Ni-MH batteries in recent years. Owing to their higher
capacity, these materials are regarded as the new generation of
materials replacing AB5 based alloys. To satisfy the requirements of
power batteries, significant efforts, including composition optimi-
zation, additives, heat treatment, surface treatment and ball milling
treatment, have been extensively conducted to improve the overall
electrochemical properties of RE-Mg-Ni-based hydrogen storage
alloys.
In addition to the above anode alloys, Mg-, Ti-V- and CoB-based
alloys have been extensively studied due to their higher energy
density in recent decades. Although there have been many suc-
cessful studies, whereby their properties were improved, it has
proven difficult to improve their hydrogenation/dehydrogenation
kinetics and rate capacities. The poor cyclability, low high-rate
dischargeability and high cost of Ti-V- and CoB-based alloys are
preventing their practical application. The stability of Mg-based
alloys in alkaline solutions still cannot meet the requirements of
industrialization. Nevertheless, once the breakthrough for the sta-
bility in electrolytes is accomplished, Mg-based hydrogen storage
alloys should make excellent negative electrode materials for Ni/
MH batteries. In any case, however, new ideas and advanced
research are still needed to develop novel electrochemical active
hydrogen storage alloys with higher energy densities, faster acti-
vation, better rate capacities and lower costs.
Acknowledgements
This work was supported by the Fund for Innovative Research
Groups of the National Natural Science Foundation of China (No.
NSFC51621001), the National Natural Science Foundation of China
Projects (Nos. 51431001) and by the Project Supported by Natural
Science Foundation of Guangdong Province of China (Nos.
2016A030312011 and 2014A030311004). The Project Supported by
Guangdong Province Universities and Colleges Pearl River Scholar
Funded Scheme (2014) is also acknowledged.
176 L. Ouyang et al. / Materials Chemistry and Physics 200 (2017) 164e178

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