i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 4 2 6 3 e4 2 7 0

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Hybrid nickel-metal hydride/hydrogen battery

Hiroki Uesato a, Hiroki Miyaoka a,b, Takayuki Ichikawa c,

Yoshitsugu Kojima a,b,*
a
Graduate School of Advanced Sciences of Matter, Hiroshima University, 1-3-1, Kagamiyama, Higashi-Hiroshima,
Hiroshima, 739-8530, Japan
b
Natural Science Center for Basic Research and Development, Hiroshima University, 1-3-1, Kagamiyama,
Higashi-Hiroshima, Hiroshima, 739-8530, Japan
c
Graduate School of Engineering, Hiroshima University, 1-4-1, Kagamiyama, Higashi-Hiroshima, Hiroshima,
739-8527, Japan

article info abstract

Article history: High capacity, high efficiency and resource-rich energy storage systems are required to
Received 25 October 2018 store large scale excess electrical energy from renewable energy. We proposed “Hybrid
Received in revised form Nickel-Metal Hydride/Hydrogen (Ni-MH/H2) Battery” using high capacity AB5-type
13 December 2018 hydrogen storage alloy and high-pressure H2 gas as negative electrode active materials. It
Accepted 17 December 2018 was experimentally confirmed that hydrogen gas can be utilized as an active material of
Available online 9 January 2019 negative electrode by the presence of the AB5-type hydrogen storage alloy. The experi-
mental average cell voltage suggested that H2 gas passed through the alloy in the form of
Keywords: atoms. The calculated gravimetric energy density of this hybrid battery increased up to 1.5
Nickel metal hydride battery times of the conventional Ni-MH battery with low content of rare-earth element which is
Metal hydride 32 wt% of the Ni-MH battery.
High dissociation pressure © 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
High-pressure hydrogen
Energy storage

metal hydride (Ni-MH) batteries, sodium-sulfur batteries,

Introduction
Energy storage technology is required for efficient utilization
of renewable energy in the world [1,2]. Developments of super
capacitors, superconducting magnetic energy storage sys-
tems, fly wheels, hydrogen-based energy storage systems,
secondary batteries, pumped storage hydroelectric systems,
and compressed air energy storage systems have been carried
out [1e4]. Among them, many researchers are conducting
study on hydrogen-based energy storage systems and sec-
ondary batteries [5e7], such as lithium-ion batteries, nickel-
redox-flow batteries, and lead-acid batteries for local leveling
of renewable energy because of their large energy density
[1e4].
Hydrogen is a resource-rich element and generated by
water electrolysis reaction. A typical hydrogen-based energy
storage system consists of a water electrolyser, a hydrogen
storage tank and a fuel cell. This system can store large
amount of electrical energy in the form of hydrogen, and then
the energy efficiency is about 40% [3].
Ni-MH battery is also famous secondary battery using
hydrogen for large scale stationary energy storage [4,8]. This

* Corresponding author. Natural Science Center for Basic Research and Development, Hiroshima University, 1-3-1, Kagamiyama,
Higashi-Hiroshima, Hiroshima, 739-8530, Japan
E-mail address: kojimay@hiroshima-u.ac.jp (Y. Kojima).
https://doi.org/10.1016/j.ijhydene.2018.12.114
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
4264 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 4 2 6 3 e4 2 7 0

battery has a good safety, cycle properties, cost performance,
compared with lithium-ion battery [9,10]. This battery stores
electric energy as the solid hydride phase of alloys. The energy
efficiency of this battery is 70e90% [11].
At the positive electrode, the electrochemical charge/
discharge reactions of Ni-MH batteries are expressed by the
following equation:
NiðOHÞ2 þ OH %NiOOH þ H2 O þ e
where, facing right and left show charge and discharge steps,
respectively. At the negative electrode, the reactions are
expressed by the equation:
M þ H2 O þ e %MH þ OH
where M and MH are a hydrogen storage alloy and the
hydrogen storage alloy absorbed hydrogen (metal hydride).
Then, the total reactions are described as follows:
NiðOHÞ2 þ M%NiOOH þ MH
At both electrodes, oxidation/reduction reactions take
place in an alkaline electrolyte such as 30 wt% KOH aqueous
solution.
AB5-type hydrogen storage alloys (AB5-type alloy) having
gravimetric capacity below 300 mAh/g (290 mAh/g, density
8.0 g/cm3) are commercially used for negative electrode active
materials [12e14]. These alloys with low plateau dissociation
pressure of 0.01e0.02 MPa at 293 K have been developed to
prevent increasing inside pressure above 0.1 MPa at
maximum working temperature of 333 K [13,15,16].
Hydrogen storage tank filled a hydrogen storage alloy
below hydrogen gas pressure of 1 MPa (MH tank) was devel-
oped for fuel cell vehicles [17]. After that, high pressure gas
technology has been advanced in the field of hydrogen [18,19].
It has been reported that “Hybrid Hydrogen Tank (High-pres-
sure MH Tank)” using hydrogen storage alloys with high
dissociation pressure and high-pressure hydrogen gas at
35 MPa can improve hydrogen storage performances such as
storage capacity and low temperature performance of the MH
tank [20,21]. The hydrogen densities of the hybrid hydrogen
tank are 1.4 times of the MH tank [20].
In this paper, we propose “Hybrid Nickel-Metal Hydride/
Hydrogen Battery” using AB5-type metal hydride with high
dissociation pressure and high-pressure hydrogen gas (H2) to
improve the energy density and decrease the amount of rare-
earth elements. The electrochemical properties were investi-
gated by the specially designed high-pressure electrochemical
cell.
La0.24Ce0.54Pr0.06Nd0.16 used for MmNi4.12Co0.79 and atomic
ratio of Mm is La0.26Ce0.53Pr0.05Nd0.16 used for MmNi4.16-
Co0.6Mn0.23Al0.05. The alloys were crushed to obtain powder
below 50 mm (median diameter: 30 mm). The MmNi4.12Co0.79
alloy was mixed with acrylic resin and carboxymethyl cellu-
lose (CMC) water solution until it was a paste. The paste was
coated and dried on a punched Ni current collector. The
negative electrode has 3.75 wt% acrylic resin and 1.25 wt%
(1) CMC per alloy. The coating amount is 40 mg/cm2 and circular
negative electrode with the diameter of 10 mm was punched
(estimated capacity: 12.5 mAh). The paste including
MmNi4.16Co0.6Mn0.23Al0.05 was coated on the Ni current
corrector using the same method of MmNi4.12Co0.79. We also
(2) used the negative electrode from commercial battery (NP2,
Primearth EV Energy Co., Ltd.). The positive electrode with the
dimeter of 10 mm was punched from the commercial battery.
The charge capacities of these cells determined by the amount
of b-Ni(OH)2 in the positive electrode are about 20 mAh.
(3)
High-pressure electrochemical cell
The high-pressure electrochemical cell (HP-cell) is shown in
Fig. 1. The cell was specially designed and assembled to
investigate the charge-discharge properties under high-
pressure hydrogen (H2, 99.99999%, Taiyo Nippon Sanso Co.)
and argon (Ar, 99.99999%, Taiyo Nippon Sanso Co.) atmo-
spheres. The inner volume of the cell was 23.8 cm3. The
pressures were measured by a pressure sensor
(520.9K0503L401W, Huba Control), and monitored by digital
indicator (KSM801, Krone Co.). Potassium hydroxide KOH
aqueous solution of 30 wt% (6 mol/L) was used with polyolefin
separator (thickness: 0.15 mm, Japan Vilene Co., Ltd.). The
punched positive electrode with diameter of 10 mm was
completely soaked in the KOH aqueous solution to prevent the
self-discharge reaction with hydrogen gas directly [22]. The
negative electrode with diameter of 10 mm was partially
soaked in the KOH aqueous solution so that the surface of the
alloy contact with H2 gas in the same way of the negative
electrode of “NickeleHydrogen (NieH2) battery” [23] using Pt-
based catalyst.
The electrochemical properties of the cell were measured
by charge-discharge test apparatus (HJ1001 SD-8, Hokuto
Denko Co.) in the voltage between 1.0 and 1.6 V with current
density of 2.54 mA/cm2 (0.1C) at 293 K and 253 K by the
mixture of sodium chloride (NaCl) and ice. The cell capacities

Experimental

Materials

The negative electrode active materials used in this study are

AB5-type alloys with high dissociation pressure such as
MmNi4.12Co0.79 and MmNi4.16Co0.6Mn0.23Al0.05 (Japan Metals &
Chemicals Co., Ltd.). The mischmetal (Mm) consists of
23.98e25.67 wt% La, 53.75e53.26 wt% Ce, 5.77e5.10 wt% Pr,
and 16.50e15.97 wt% Nd. Atomic ratio of Mm is Fig. 1 e Schematic diagram of specially designed high-
pressure electrochemical cell (HP-cell).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 4 2 6 3 e4 2 7 0
of these cells determined by the amount of b-Ni(OH)2 in the
positive electrodes are about 20 mAh. Before the electro-
chemical measurements, positive electrode and negative
electrode were activated by a charging and discharging under
3.0 MPa H2 atmosphere.
Characterization
Pressure-composition-temperature (PCT) profiles were
measured under H2 pressure of 0.001e5.0 MPa and at
273e293 K by the Sievert type apparatus (Suzuki Shokan Co.,
Ltd.).
Powder X-ray diffraction (XRD) measurements were car-
ried out to characterize the structure of electrode active ma-
terials after charge and discharge. The XRD patterns were
measured by RINT-2500V (Rigaku Co.) in which the X-ray
source is Cu-Ka with 40 kV/200 mA of output power. All the
samples were placed on the glass plates and covered by pol-
yimide sheets (Kapton®, Du Pont-Toray Co., Ltd.) to prevent
the exposure to air. Hydrogen and oxygen released from
electrodes during charge was detected by gas chromatography
(GC-14B, Shimadzu Co., Ltd.) at 0.10 MPa Ar atmosphere.
Results
Concept
Conceptive picture of the “Hybrid Nickel-Metal Hydride/
Hydrogen (Ni-MH/H2) Battery” is shown in Fig. 2. This battery
consists of positive electrode using Ni(OH)2 as a active mate-
rial and hybrid negative electrode, which is composed of
hydrogen storage alloy with high dissociation pressure (M)
and high-pressure H2 as active materials. The plateau disso-
ciation pressure of the MH is above 0.1 MPa and the gravi-
metric hydrogen density is 1.4e1.5 wt% [24].
The negative electrode reaction is divided into two re-
actions, although the positive electrode reaction is identical
with the commercial Ni-MH battery. One reaction represents
hydrogen insertion and deinsertion in the alloy during change
and discharge. The other reaction represents hydrogen gas is
desorbed and absorbed during the charging and discharging in
the vessel, respectively.
Previously, “Nickel-Metal Hydride/Hydrogen Hybrid Bat-
tery using Alkali Ion Conducting Separator” which is a com-
bination of hydrogen storage alloy and hydrogen dissociation
catalyst such as platinum, was patented [25]. In this patent,
Fig. 2 e Conceptive picture of “Hybrid Nickel-Metal
Hydride/Hydrogen (Ni-MH/H2) battery”.
4265
the current carrying species in electrolyte were exclusively
alkali metal ion such as sodium ion (Naþ). However, in our
concept, the current carrying species in electrolyte is hy-
droxide ion (OH). Additionally, hydrogen storage alloy with
high dissociation pressure is utilized as both of a negative
electrode active material and a hydrogen dissociation catalyst
in our concept.
AB5-type alloy with high dissociation pressure leads large
volumetric capacity of 3300e3400 mAh/cm3 assuming that the
density is 8.6 g/cm3 [24], while the calculated gravimetric ca-
pacity is 380e400 mAh/g according to a general method in
reference [26]. However, high-pressure H2 gas has large
gravimetric capacity of 26,600 mAh/g, while the volumetric
capacities at 293 K are 629 mAh/cm3 (0.0237 g/cm3), 475 mAh/
cm3 (0.0179 g/cm3), and 207 mAh/cm3 (0.00780 g/cm3) under
35 MPa, 25 MPa, and 10 MPa, respectively [27]. Thus, this
hybrid battery is expected to improve the gravimetric energy
densities of Ni-MH by changing the molar ratio of the alloy and
compressed hydrogen gas under various pressure.
Metal hydride
Fig. 3 shows pressure composition isotherm (PCI) for hydrogen
desorption process of MmNi4.12Co0.79 at 293 K. The PCI of the
hydrogen storage alloy used in commercial Ni-MH batteries is
also shown as a reference. The plateau dissociation pressures
were obtained by an equilibrium pressure at desorbing
hydrogen which is 50% of the maximum absorbed hydrogen
amount [24]. The dissociation pressure of MmNi4-12Co0.79 is
2.0 MPa at 293 K and has a higher than that of the AB5-type
alloys in the commercial batteries (0.012 MPa at 293 K).
The dissociation pressure of MmNi4.16Co0.6Mn0.23Al0.05 is
0.35 MPa at 293 K (Supplementary Fig. 1). XRD indicates that
MmNi4.12Co0.79 and MmNi4.16Co0.6Mn0.23Al0.05 have hexagonal
CaCu5 type crystal structure [28,29], which is similar to AB5-
type alloy in the commercial batteries (Supplementary Fig. 2).
The lattice constants of these alloys are smaller than the value
Fig. 3 e Pressure composition isotherms (PCIs) of
MmNi4.12Co0.79 and AB5-type alloy in the commercial
batteries at 293 K.
4266 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 4 2 6 3 e4 2 7 0
of AB5-type alloy in the commercial batteries. It has been re-
ported that the dissociation pressure of AB5-type alloys in-
creases with decreasing of the cell volume [26,30,31].
MmNi4.12Co0.79 and MmNi4.16Co0.6Mn0.23Al0.05 also follow the
trend (cell volume of MmNi4.12Co0.79: 0.0082 nm3/a0 ¼ 0.484
nm/c0 ¼ 0.406 nm, cell volume of MmNi4.16Co0.6Mn0.23Al0.05:
0.0084 nm3/a0 ¼ 0.497 nm/c0 ¼ 0.394 nm, cell volume of
AB5etype alloy in the commercial batteries: 0.0087 nm3/
a0 ¼ 0.504 nm/c0 ¼ 0.397 nm). The reversible hydrogen ca-
pacities between 5 and 103 MPa is 1.4e1.5 wt%. Theoretically
calculated electrochemical capacity was 380e400 mAh/g. This
capacity was higher than a value of the AB5-type alloy in
commercial battery (below 300 mAh/g). The standard
enthalpy change (DH) and the standard entropy change (DS) of
hydrogen desorption reactions were estimated by van't Hoff
equation shown in Eq. (4) [21,32].
PeqH2 DH DS
ln ¼ 
P0 RT R
where PeqH is the dissociation pressure of hydrogen storage
2
alloy (MPa), P0 is standard pressure (0.101 MPa), R is gas con-
stant (8.314 J/K$mol), T is temperature (K).
The standard enthalpy change (heat of formation) DH and
the standard entropy change DS were 25.4 kJ/mol-H2 and
108 J/K$mol-H2, respectively. The DH and the DS of
MmNi4.16Co0.6Mn0.23Al0.05 were 30.5 kJ/mol-H2 and 115 J/
K$mol-H2, respectively. The absolute values of the DH are
small compared with the conventional AB5-type alloy used for
the Ni-MH batteries (DH:34.8 kJ/mol-H2 DS:101 J/K$mol-H2).
Those values of DS are smaller than entropy of H2 (131 J/
K$mol-H2) [27].
Fig. 4 e Charge (upper) and discharge (lower) curves of HP-
cell using MmNi4.12Co0.79 as a negative electrode material
with current density of 2.54 mA/cm2 (0.1C) at 293 K, (C) gas
pressure in HP-cell under 0.1 MPa Ar during charge.
Electrochemical properties
Upper figure of Fig. 4 shows charge curves of the high-pressure
electrochemical cell (HP-cell) composed of b-Ni(OH)2 and
MmNi4.12Co0.79 under H2 of 1.0 and 3.0 MPa which is below and
above the dissociation pressure of the alloy, and Ar of
0.10 MPa. The charge experiment was carried out up to the
capacities of 20 mAh which is determined by theoretical ca-
pacity of positive electrode in the cell. The charge curves
under H2 and Ar have similar shape, suggesting that the same
electrochemical reaction would proceed independent of the
H2 pressure in the cell. Under Ar atmosphere of 0.10 MPa, gas
pressure increases with the charging. The released gas during
the charging process was analyzed by a gas chromatography.
As a result, the released gas is H2 (Supplementary Fig. 3). The
partial pressure of H2 in the HP-cell was increased from 0 to
0.035 MPa during the charge measurement under 0.10 MPa Ar.
This H2 amount estimated from the pressure gain
(4)
approximately corresponds to the formation of NiOOH from
Ni(OH)2 in the positive electrode. However, the molar ratio of
H/Ni(OH)2 is estimated to be 0.82. It is presumed that the small
amount of hydrogen (molar ratio: 0.18) is electrochemically
absorbed in the alloy even if below the dissociation pressure,
or it was remained in electrochemically inactive Ni(OH)2.
“Fuel Cell/Battery (FCB)” which combined the Ni-MH bat-
tery and fuel cell system, has been proposed to realize high
capacity energy storage [33,34]. At the FCB system, hydrogen
and oxygen are released by over charge. At the Ni-MH/H2
battery proposed in this work, only hydrogen is released by
full charge and released gas is different from FCB system.
Lower figure of Fig. 4 also shows discharge curves of the
HP-cell composed of NiOOH and the hydrogenated
MmNi4.12Co0.79 with high-pressure H2 at 3.0 MPa which is
above the dissociation pressure of the alloy. The discharge
capacity of the cell is 17.4 mAh, although the theoretical ca-
pacity of MH was 12.5 mAh without gaseous H2. The discharge
capacity was changed from 17.4 to 18.3 mAh by repeated
measurements (Supplementary Fig. 4). Namely, H2 can be
utilized in the discharging process. The capacity was down to
12.5 mAh by soaking of MH in KOH aqueous solution
(Supplementary Fig. 4). This indicates that the surface of the
alloy contacted with H2 is a key to utilize the H2. The discharge
capacities are drastically decreased at 1.0 MPa of H2 and
0.10 MPa of Ar, which is below the dissociation pressure. The
small amount of discharge capacity below the dissociation
pressure also suggests that the alloy includes hydrogen atom
because hydrogen release rate is slow. Noble metal catalysts
such as Pt is required as catalysts for H2 dissociation in the Nie
H2 battery [23,35]. On the other hand, the above results suggest
that AB5-type alloy plays a role as a hydrogen storage material
and catalyst for H2 dissociation at above the dissociation
pressure in the proposed Ni-MH/H2 battery. Thus, the high-
cost catalysts are not necessary.
Fig. 5 shows XRD patterns of the positive electrodes after
the charging and discharging processes. The peaks corre-
sponding to Ni current corrector was observed for all samples
as a background. XRD pattern of as-purchased positive elec-
trode shows peaks at 2q of 19.03, 33.09, 38.51, 59.07, and 62.67 .
These peaks originate in (001), (100), (101), (110), and (111)
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 4 2 6 3 e4 2 7 0 4267

RT PeqH2
E ¼ E0  ln 0 (5)
2F P
where PeqH is the dissociation pressure of hydrogen storage
2
alloy (MPa), P0 is standard pressure (0.101 MPa), R is gas con-
stant (8.314 J/K$mol), T is temperature (K), F is Faraday con-
stant (96485C/mol).
E of hydrogen storage alloy is 0.828 V vs SHE (Standard
Hydrogen Electrode: þ0.000 V) [4]. The electromotive force of
the cell (EEMF) is determined by the theoretical potential dif-
ference of the electrodes using the hydrogen storage alloys
and Ni(OH)2 (þ0.52 V vs SHE) [37].

Eemf ¼ 0:52  E (6)

The average cell voltage which is assumed to be propor-

tional to the Eemf (open circuit voltage), was defined as the
arithmetic mean of the charge and discharge voltages at 50%
of each capacity. Fig. 6 shows the dependences of the average
cell voltage on dissociation pressure of the negative electrode
material at 293 K and 253 K. The EEMF of the cell is also shown
in the same Fig. 6 as a function of the dissociation pressure of
Fig. 5 e XRD patterns of the positive electrodes as AB5-type alloy.
purchased and after charge/discharge conditions under H2 The experimental average cell voltages are determined by
and Ar gas together with the data of b-Ni(OH)2 (JCPDS file the thermodynamic parameters of H2, whether the electro-
No. 00-014-0117), b-NiOOH (JCPDS file No. 00-006-0141), g- chemical reaction proceeds at the interface between the KOH
NiOOH (JCPDS file No. 00-006-0075), Ni (JCPDS file No. 00- aqueous solution and H2 via the surface of AB5-type alloy.
004-0850). However, Fig. 6 shows that the experimental average cell
voltages linearly increase with the logarithm of the dissocia-
tion pressure. The slope is similar to the dependence of EEMF
planes of b-Ni(OH)2 having Cd(OH)2 type hexagonal structure on logarithm of dissociation pressure. This result suggests
[36]. The interlayer distance of b-Ni(OH)2 is 0.472 nm. After that the electrochemical reaction proceeds at the interface
charging under 3.0 MPa of H2 and 0.10 MPa of Ar, XRD patterns between the KOH aqueous solution and the AB5-type alloy.
of positive electrode show peaks at 2q of 18.97e18.95, 38.61,
and 66.19e66.07 . Those 3 peaks corresponds to diffraction
from (001), (002), and (110) planes of b-NiOOH [37,38]. The
peaks at 19.03 of b-Ni(OH)2 shifts a little to lower angle of
18.97e18.95 after the charging, and then the interlayer dis-
tance of b-NiOOH is 0.474 nm. It is considered that the
expansion of (001) plane of NiOOH is suppressed in the posi-
tive electrode by additives [38]. The peaks at 2q of 12.81e12.83
and 25.81e25.67 originate in (003) and (006) planes of g-
NiOOH, respectively. The interlayer distance of g-NiOOH is
0.694e0.695 nm. b-Ni(OH)2 was changed to b- and small
amount of g-NiOOH after the charging process under 3.0 MPa
H2 and 0.10 MPa Ar. The formation of g structure can be
explained by the overcharge [36]. Small amount of Ni(OH)2 is
remained after the charging. After discharging, b- and g-
NiOOH is changed to b-Ni(OH)2 at H2 of 3.0 MPa.
For the negative electrodes, the XRD patterns of the nega-
tive electrode active materials after the charging and dis-
charging processes show substantially same patterns. AB5-
type metal hydride with high dissociation pressure is unstable
under XRD measurement condition at atmospheric pressure
(Supplementary Fig. 5).
Thermodynamic parameters such as hydrogen dissocia-
tion pressure P of the hydrogen storage alloys are correlated
with theoretical potential (E) [32,39]. The E of MmNi4.12Co0.79 is Fig. 6 e The dependences of the average cell voltage and
calculated by the following equation. EEMF on dissociation pressure of the AB5-type alloys.
4268 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 4 2 6 3 e4 2 7 0
Fig. 7 e The dependence of the cell voltage on H2 pressure
in the HP-cell at 293 K, using MmNi4.12Co0.79 (red) and AB5-
type alloy in the commercial batteries (black) as negative
electrode materials. (For interpretation of the references to
colour in this figure legend, the reader is referred to the
Web version of this article.)
The potential of negative electrode can be approximately
determined by thermodynamic parameters of AB5-type alloy
such as the dissociation pressure.
Additionally, the experimental average cell voltage was
measured under several H2 pressure. Fig. 7 shows the de-
pendences of the average cell voltage on H2 pressure. The
experimental average cell voltages used MmNi4.12Co0.79 are
approximately constant despite of internal pressures in the
cell (Average: 1.41 V). In the case of using the commercial
negative electrode, it is also indicated the similar trend exists
(Average: 1.36 V).
The difference in the average of the cell voltage by the
negative electrode materials corresponds to the results in Fig. 6.
It is indicated that the electrochemical reaction doesn't proceed
at the interface between KOH aqueous solution and H2. This
result is different from NieH2 battery using Pt-based catalyst [4].
Discussion
The above results about experimental average voltage of the
cell suggested that hydrogen gas is released after passing
through the alloy in the form of atoms and the gas is disso-
ciated into atoms and pass through the alloy during the
charging and discharging processes, respectively.
Therefore, at the later stage of charge and initial stage of
discharge, the overall reaction can be expressed by the
following equation:
1x
ð1  xÞNiðOHÞ2 þ xMH% H2 þ xMH þ ð1  xÞNiOOH
2
(7)
Number of H atom in MH
x:
Number of H atom in MH and gas
where x is the ratio of the number of hydrogen atoms in MH to
the total number of hydrogen atoms in MH and compressed
hydrogen. x is in the regions of 0 < x < 1. Hydrogen molecules
dissociate into atoms and pass through MH during
discharging.
At the initial stage of charge and at the later stage of
discharge, the conventional reaction according to the equa-
tion below occurs [4]:
xNiðOHÞ2 þ xM%xNiOOH þ xMH (8)
The total reaction is expressed by the following equation.
1x
NiðOHÞ2 þ xM%NiOOH þ H2 þ xMH ð0 < x < 1Þ (9)
2
We have calculated theoretical capacities of the hybrid
battery combining the AB5-type alloy with high dissociation
pressure and compressed hydrogen, together with the data of
Ni-MH battery. At an operating pressure of 35 MPa at 293K, the
volume of a tank (10 L) for gaseous hydrogen allows storage
capacity of 0.23 kg-H2. The assumed density of alloys with
high dissociation pressure is 8.6 gcm3. When the tank (10 L) is
filled with the alloy of 0e43 kg (packing ratio: 0e50%), the
gravimetric capacities Cng and volumetric capacities, Cnv are
shown in Fig. 8.
Cng decreases with the packing ratio and has 471 mAh/g at
50%. Cnv increase linearly with the packing ratio of the alloy
and has 2030 mAh/cm3 at 50%. Cng and Cnv of negative elec-
trode active materials such as AB5-type alloy with high
dissociation pressure including compressed hydrogen at
35 MPa and conventional AB5-type alloy used for Ni-MH bat-
tery are 801 mAh/g (1049 mAh/cm3) and 290 mAh/g
(1160 mAh/cm3), respectively. Here, the volume ratio of the
alloy to the compressed hydrogen is 15%.
Fig. 8 e The dependences of gravimetric/volumetric
densities on packing ratio.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 4 2 6 3 e4 2 7 0
Table 1 e Calculated energy densities of hybrid and Ni-
MH batteries without binder, electrolyte, current
collector, separator and vessel.
Energy density Hybrid battery Ni-MH battery
Eg/Wh/kg 275 189
Ev/Wh/L 497 516
Assuming that the capacity of the negative electrode active
materials are equal to positive electrode active materials [40],
then, gravimetric and volumetric energy densities Eg (Wh/kg),
Ev (Wh/L) of the battery are expressed by the following
equation,
1:3Cng
Eg ¼ 92:7Cng
26800
þ1
1:3Cnv
Ev ¼ 92:7Cnv 1
26800 2:08
þ1
Here, we used battery voltage of 1.3 V. Molecular weight of
Ni(OH)2 is 92.7 and the quantity of electricity per electron is
26800 mAh/mol. The packing density of Ni(OH)2 is 2.08 g/cm3,
by assuming that the packing ratio is 50%. We have calculated
the gravimetric and volumetric energy densities of the hybrid
and conventional Ni-MH batteries according to Eqs. 10 and 11.
Table 1 shows energy densities of the hybrid and the Ni-MH
batteries without binder, electrolyte, current collector, sepa-
rator and vessel.
The gravimetric density increases up to 1.5 times, although
the volumetric density has similar value. The required
amount of AB5-type alloys in the hybrid battery decreases
down to 32 wt% compared with the Ni-MH battery. As a result,
the amount of rare-earth element can be decreased.
The hydrogen-based energy storage system is composed of
electrolyser, hydrogen storage tank, and fuel cell. The total
efficiency is about 40%. The energy storage and generation
efficiency of Ni-MH battery is 70e90% [11]. In this work,
coulombic efficiency is 87e92% and energy efficiency is
74e76% (see Fig. 4). The energy efficiency is similar to Ni-MH
battery and two times larger than that of the hydrogen-
based energy storage system.
Conclusion
We proposed “Hybrid Nickel-Metal Hydride/Hydrogen (Ni-
MH/H2) Battery” using AB5-type metal hydride (MH) with high
dissociation pressure (>0.1 MPa) and high-pressure hydrogen
gas (H2) as negative electrode materials. The electrochemical
properties under high-pressure H2 atmosphere were investi-
gated by the high-pressure electrochemical cell. As a result,
hydrogen gas was reversibly utilized for charge and discharge
reaction at above the dissociation pressure of the AB5-type
alloy. It is experimentally demonstrated that the concept of
the hybrid battery can be realized.
The cell voltage obtained by the experiments was consis-
tent with the theoretical voltage estimated by dissociation
pressure of the AB5-type alloys. This indicates that hydrogen
4269
gas is released after passing through the alloy in the form of
atoms, and the gas is dissociated into atoms and pass through
the alloy during the charging and discharging processes,
respectively.
It is expected that this battery will provide high capacity
and high efficiency energy storage system reduced rare-earth
element.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2018.12.114.
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