Energy 97 (2016) 498e505

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Energy
journal homepage: www.elsevier.com/locate/energy

Characteristics of a sintered porous NieCu alloy cathode for hydrogen

production in a potassium hydroxide solution
Linping Yu a, b, Ting Lei a, Bo Nan a, Yao Jiang a, *, Yuehui He a, C.T. Liu c
a
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, PR China
b
School of Chemistry and Biology Engineering, Changsha University of Science and Technology, Changsha 410114, PR China
c
Center for Advanced Structural Materials, College of Science and Engineering, City University of Hong Kong, Hong Kong

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

Article history: A porous NieCu alloy with a most probable pore size of 2.4 mm and an open porosity over 31.5% was
Received 6 May 2015 synthesized by step sintering pressed compacts consisted of mixed Ni and Cu powders in a vacuum
Received in revised form furnace. The electrocatalytic activity and stability of the fabricated porous NieCu alloy as cathode for the
30 December 2015
HER (hydrogen evolution reaction) in 6.0 mol/L potassium hydroxide solution were investigated by
Accepted 31 December 2015
Available online xxx
cathodic currentepotential curves, CV (cyclic voltammetry) and EIS (electrochemical impedance spec-
troscopy) techniques. Results show that the onset potential of the porous NieCu for HER greatly shifts to
the positive direction compared with the dense Ni and dense NieCu alloy. The electrochemical activation
Keywords:
Porous NieCu alloy
energy is determined to be 26.7 kJ mol
1 for the porous NieCu alloy, against 44.1 kJ mol
1 and
Powder metallurgy 32.6 kJ mol
1 for the dense Ni and dense NieCu alloy, respectively. The increased activity of the porous Ni
Hydrogen evolution reaction eCu alloy for HER is related to the micro-porous structure as well as synergistic interaction of Ni and Cu.
Electrocatalytic activity Besides, the fabricated porous NieCu alloy displays good corrosion resistance in potassium hydroxide
Stability solution during the immersion test, which makes it possible for long-time running as cathode in the
process of hydrogen evolution reaction.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Compared with natural gas reforming or gasification of coal and
petroleum coke, the water electrolysis is a sustainable technology
to produce hydrogen which mainly relies on renewable energy
sources [1]. The development of lowcost cathode materials with
high electrocatalytic activity has long been an important part of the
research topics in hydrogen production by water electrolysis [2e4].
It's almost universally accepted that an increase in the electrode
catalytic activity can be carried out by enlarging the actual surface
area or improving its intrinsic catalytic activity.
Various studies have attempted to improve the electrocatalytic
activity for HER (hydrogen evolution reaction) by introducing other
components into Ni as cathodes, for its low-cost characteristic and
special electron structure as catalyst [5e9]. Although the multi-
component materials show higher overall electrocatalytic activity
than pure Ni, the reasons for this improvement are usually
* Corresponding author. Tel./fax: þ86 73188836144.
E-mail address: jiangyao@csu.edu.cn (Y. Jiang).
different. Among these researches, for instance, the superior ac-
tivity for NieMo, NieW and NieFe in acidic media toward HER was
found to be an increased surface roughness by leaching the active
component [6], and the same situation for NieZn [7], NieAl [8], and
NieMo [9] in alkaline solutions. Alternatively, the synergistic
interaction between components is proven to explain the increased
intrinsic activity of cathodes in HER. C. Lupi et al. [10] have prepared
various compositions of NieCo alloys on aluminum net supports by
electro-deposition, obtaining a large value of exchange current
density and low hydrogen over-potential in the case of Ni con-
centrations ranging from 35 to 59 weight percent. Kellenberger
et al. [11] have confirmed that the addition of Ti to Ni significantly
reduces the electrochemical activation energy for the HER. The
activity improvements are ascribed to a pronounced synergy be-
tween components as a consequence of the change in the electronic
properties; and similar findings also exist between Co and Ni [12],
Ni and CoeW [13], Ni and CeO2 [1], etc.
Electro-deposition is a simple and inexpensive method to
combine different components for purpose of synergy, as well as to
enhance the actual surface of materials, thus it has traditionally
been used to develop new cathodes for hydrogen evolution

http://dx.doi.org/10.1016/j.energy.2015.12.138
0360-5442/© 2016 Elsevier Ltd. All rights reserved.
 L. Yu et al. / Energy 97 (2016) 498e505
reaction. Nevertheless, it is hard to ensure the adherence of the
deposit with the substrate while maintaining the composition of
the deposit [14] by this technique. Despite the large numbers of
cathodes reported so far, it should be emphasized that for the
technological applications besides the electrocatalytic activity, the
stability of the cathode materials in HER should also be paid
attention to.
Powder metallurgy is found to be a straightforward and
reasonably effective approach turning the bulk alloys with excel-
lent properties (e.g. corrosion resistance, wear ability, high strength
and hardness) into porous counterparts [15e17]. The Monel alloy is
well-known for its superior corrosion resistance in a reducing
environment than pure Ni, and than pure Cu in an oxidizing one.
Monel is widely used in nuclear and chemical industry [18e20].
Since the component for Monel is a binary Ni/Cu body with a small
amount of additions, to avoid the interference of the additions on
pore forming process, the binary Ni/Cu system with atomic ratio of
2:1 (Ni:Cu) is selected to fabricate a porous structure by powder
metallurgy.
Moreover, there are continuing reports about the synergistic
effect between Ni and Cu on HER in alkaline water [21e24], most of
which are based on electro-deposition method. The enlarged sur-
face area and a fairly stable porous structure of porous NieCu alloy
obtained by powder metallurgy, further enlighten the authors to
explore its electrocatalytic performance as electrodes.
Present work concerns the electrocatalytic activity as well as the
stability of porous NieCu binary alloy as cathodes for the HER in
6.0 M KOH solution. The surface morphology and composition of
the prepared porous NieCu alloy cathode are analyzed using SEM
(scanning electron microscopy) and XRD (X-ray diffraction) tech-
niques, respectively. The kinetics of the HER on this electrode ma-
terial is studied by steady-state polarization and electrochemical
impedance spectroscopy measurements (EIS). Meantime, the sta-
bility towards HER and corrosion behavior of the porous NieCu in
alkaline medium during long-term operation are also investigated
in detail.
2. Experimental procedure
2.1. Preparation of porous NieCu alloy cathode
The commercially available nickel (median diameter: 8.2 mm)
and copper powders (median diameter: 19.5 mm) with purities
more than 99.7wt.% were mixed to obtain a uniform mixture of Ni-
rich (67wt.%Nie33wt.%Cu) composition. Flake compacts with di-
mensions of 55.0 mm  9.0 mm  (1 ± 0.1 mm) were cold pressed
at uniaxial pressure of 100 MPa. Sintering was performed in the
furnace with vacuum of 1.0  10
4 Pa. The compacts were buried in
alumina balls for homogenous heating. The heating rate was
controlled within 5  C per minute, at temperatures of 700, 800,
1000 and 1100  C for durations of 1 h followed by furnace cooling to
room temperature.
The electric-arc melted dense NieCu alloy (same chemical
composition as porous NieCu) and the dense Ni were selected for
comparative study. All the samples used for following tests were
rinsed with deionized water in an ultrasonic cleaner for 30 min,
then degreased in anhydrous alcohol, and finally dried up in vac-
uum oven at 75  C for 2 h prior to use.
2.2. Characterization of the porous NieCu alloy cathode
The phase and crystal structure of the sintered porous NieCu
samples were analyzed by XRD (D/max 2550VB with Cu Ka radia-
tion). The morphology of the material was characterized by SEM
(JSM-6360LV, 20 kV). The pore size distribution was determined by
499
the use of mercury intrusion (Pore Master 33 GT, Quantachrome
Instruments). Archimedes principle was employed to measure the
open porosity of porous samples. The N2 permeate flux of porous
structure was measured through bubble test [25]. The tensile
strength and transverse rupture strength of the porous NieCu alloy
were tested by an Electric Servo-hydraulic Material Test system
(INSTRON 3369).
CV (Cyclic voltammetry) curves, cathodic polarization curves
and electrochemical impedance spectroscopy (EIS) techniques
were used to characterize the electrochemical performance of the
porous NieCu alloy electrode in 6.0 M KOH solution, with a geo-
metric surface area of 1.0 cm2 exposed to the solution. Pt foil and
saturated calomel electrode (SCE) were used as the counter elec-
trode and the reference electrode, respectively. A salt bridge made
by polytetrafluoroethylene was used to reduce the liquid junction
potential. The Luggin capillary was arranged as closely as possible
to the working electrode in order to minimize errors due to IR drop
in solutions. Steady-state CV curves were recorded in 6.0 mol/L
KOH solution at a series of scan rates of 0.01, 0.05, 0.10, 0.20, 0.30
and 0.40 V s
1. Cathodic polarization curves were recorded in po-
tassium hydroxide solution at a scan rate of 0.001 V s
1. The EIS
measurements were conducted at different cathodic overpotentials
in the frequency range of 100 kHze0.01 Hz, with the perturbation
amplitude of 0.005 V.
3. Results and discussion
3.1. Characterization of porous NieCu alloy cathode
The surface morphology of the green compact and the sintered
NieCu alloy is exhibited by SEM, as shown in Fig. 1a and b,
respectively. Mixed metal powders are merely mechanically
pressed together in the green compact, which has a low strength
and an open porosity of 15.2%. The porosity of green compact is
mainly composed by the interstitial pores formed between powder
particles. Powder metallurgy affords good controls of the porous
structure of porous materials. The pore morphology is dependent
on factors such as pressing pressure, sintering conditions (tem-
perature and time), particle size and shape of metal powder.
Abundant interconnected pores and the generally smooth pore
walls can be seen in the sintered NieCu alloy porous structure
(Fig. 1b), which has a most probable pore size of 2.4 mm, measured
by mercury intrusion method. The N2 permeate flux is
28.5 m3 h
1 kPa
1 m
2 for the thickness of 1.8 mm by bubble test.
The pore size distribution (Fig. 1c) displays a significant narrow
peak at the size of 2.4 mm, indicating a homogenous porous
structure is formed. The XRD patterns of the fabricated porous
NieCu alloy and green compact are shown in Fig. 1d. A NieCu solid
solution alloy is obtained after sintering, which has the same FCC
structure as that of pure Ni and Cu.
The decrease of the surface freedom energy of powder com-
pacts, together with the Kirkendall effect caused by the huge
discrepancy of mutual diffusion coefficients between Ni and Cu,
determines the evolution of pores in the porous NieCu in the sin-
tering process [26e28]. The porous samples in this research have
an open porosity over 31.5% and closed porosity of less than 2.7%,
and the numerous interconnected pores considerably enlarge the
actual surface area of porous NieCu alloy.
3.2. Electro-catalytic evolution of hydrogen on porous NieCu alloy
cathode
3.2.1. Actual surface area of electrodes
The roughness factor of the fabricated porous NieCu alloy, dense
Ni and dense NieCu alloy are evaluated by comparing their double
500 L. Yu et al. / Energy 97 (2016) 498e505

Fig. 1. Surface morphology of NieCu compacts before (a) and after (b) sintering; (c) Pore size distribution of the sintered porous NieCu alloy; (d) X-ray diffraction patterns of the
sintered porous NieCu alloy and the green compact containing Ni and Cu.

layer capacitance measured by cyclic voltammogram (CV) with
ideal value 20 mF cm
2 [29]. Fig. 2a is the representative CV curves
of the porous NieCu in 6.0 M KOH solution at different sweeping
rates. It is depicted that stationary double layer currents appear
between the potential ranging from
0.30 V to
0.18 V vs. SCE. In
this region, the average of capacitive current (jdl;ave ) is proportional
to the double layer capacitance (Cdl), and the average of double
layer current densities as a function of potential sweep rate can be
described as followed [30,31]:
The capacitances of the three electrodes can be estimated from
the slopes in the plots of current density against sweeping rate, as
shown in Fig. 2b. The relative magnitude of the respective rough-
ness factor, Rf, is considered to be the actual active surface area of
the catalytic material [31]. The calculated results are summarized in
Table 1. It shows that the actual surface of the sintered porous
NieCu fabricated by powder metallurgy increases tremendously
than the dense NieCu alloy, owing to the interconnected micro-
sized pores formed during the sintering process.

jjc j þ jja j dE 3.2.2. The hydrogen evolution performance of porous NieCu alloy
jdl;ave ¼ ¼ Cdl (1) cathode
2 dt
The cathodic polarization curves for HER of three electrodes in
where jc and ja are cathodic and anodic current density, 6.0 M KOH are illustrated in Fig. 3. The onset potential of HER
respectively. mostly reflects the reaction activity of cathode in water electrolysis

4.0
Current density (10 A/cm2)

Current density (10 A/cm2)

6.0
(a) (b) Porous Ni-Cu
4.0
3.0 Dense Ni
-4

-4

2.0 Dense Ni-Cu

0 2.0
1mV
-2.0 5mV
10mV 1.0
-4.0 20mV
30mV
-6.0
40mV
0.0
-0.18 -0.20 -0.22 -0.24 -0.26 -0.28 -0.30 -0.32
0.00 0.01 0.02 0.03 0.04
Potential/V (vs.SCE) Scan rate (V•s )
-1

Fig. 2. (a) Cyclic voltammograms in the double layer region of the sintered porous NieCu alloy at different scan rate; (b) the mean current density as a function of scan rate for three
electrodes.
 L. Yu et al. / Energy 97 (2016) 498e505 501

Table 1
Electrochemical properties of the porous NieCu alloy electrode (compared with dense NieCu alloy and Ni).

Electrode Cdl (mF/cm2) Rf Tafel slope (mV/dec) j0 (mA/cm2) j0/Rf (mA/cm2) Onset potential (V/vs. SCE)

Dense Ni 342 17.1 107 7.32  10
3 4.28  10
4
1.57

Dense NieCu 310.0 15.5 149 0.04 2.58  10
3
1.47
Porous NieCu 9021.5 451.0 218 1.01 2.24  10
3
1.39

process. For this research, it is obtained by intercepting the Obviously, the presence of Cu leads to a considerable increase of
extrapolated current baseline with the prolonged tangent at the intrinsic activity, as shown by the j0/Rf value of dense NieCu, which
liner region of cathodic polarization curve. The gradient dj=dE of is about 5 times higher than that of dense Ni electrode. As expected,
the porous NieCu cathode is much steeper than the dense NieCu the porous NieCu electrode shows a better activity than dense
and dense Ni in the hydrogen evolution process. Furthermore, the counterpart during the HER owing to the increase of actual surface
measured onset potential of porous NieCu for HER is much more area, despite the high Tafel slope. The greater hydrogen evolution
positive, which makes generation of hydrogen easily under lower activity of porous NieCu alloy for HER can be ascribed to both the
overpotential, as compared with dense NieCu and dense Ni elec- large electrochemical actual surface area and the synergistic effect
trodes. At the polarization potential of
1.6 V, the cathodic current after alloying Ni with Cu.
density of porous NieCu is 151 mA cm
2, about 120 mA cm
2 and Generally, the value of Tafel slope is related to the mechanism of
65 mA cm
2 higher than that of dense Ni and dense NieCu alloy, hydrogen evolution reaction in alkaline solution. As shown in
respectively. Table 1, the Tafel slopes for the porous NieCu, dense NieCu and Ni
The apparent exchange current density j0 can directly reflect the electrode are 218, 149 and 107 mV dec
1, respectively. The Tafel
depolarization ability of cathode for HER, which can be reasonably slope for porous cathode is obviously higher than dense cathodes
taken as a measurement of the catalytic efficiency. It is derived during HER. The increase of Tafel slope during hydrogen evolution
directly from the intercept by the extrapolation of Tafel slope to
equilibrium potential based on its relationship with overpotential
described as [32]:
(a) 140
h ¼ a þ b log j0 (2) -0.25V
120 -0.28V
Where h is the overpotential for HER; a and b are Tafel intercept
Rs -0.30V
and Tafel slope, respectively. The effective exchange current density 100
-0.32V
(j0/Rf) based on the actual surface area Rf offers a more compre- R1 R2 -0.35V
80
Z' (ohm)

hensive understanding about the electro-catalysis intrinsic activ-

ities of cathode material [33]. The effective exchange current
densities for three electrodes are calculated, as shown in Table 1. 60
The effective exchange current density (j0/Rf) for HER on the
porous NieCu alloy electrode is 2.24  10
3 mA cm
2, obviously 40
higher than the dense Ni electrode 4.28  10
4 mA cm
2, showing
that the intrinsic activity of the porous NieCu alloy is remarkably 20
higher than dense Ni. Besides, this value is comparable to those
found for NieCo alloys [12] in 30% KOH at 25  C, chemically treated 0
NieZr electrode [34] and porous NieTi in 1.0 M NaOH at 25  C [35]. 0 20 40 60 80 100 120 140
However, it is lower than that of the Ni-Mn-Zn [36], electro-
deposited Ni-Mo [9] and NieCo in situ activated with Mo [12].
Z' (ohm)

0.00 (b) 100

80
Current density (A/cm2)

-0.05
-Phase (degree)

60
-0.10
40
Porous Ni-Cu
-0.15 Dense Ni -0.25V
20 -0.28V
Dense Ni-Cu
-0.30V
-0.20 0 -0.32V
-0.35V
-0.25 -20 -2 -1 0 1 2 3 4 5
-1.8 -1.6 -1.4 -1.2 -1.0 10 10 10 10 10 10 10 10
Potential/V (vs. SCE) Frequency (Hz)
Fig. 3. The cathodic linear sweep curves recorded on three electrodes for hydrogen Fig. 4. The Nyquist (a) and Bode (b) diagrams for porous NieCu at different electrolysis
evolution in 6.0 M KOH at the scan rate of 1 mV s
1. potentials; inset in (a): the corresponding equivalent circuit model.
502 L. Yu et al. / Energy 97 (2016) 498e505

Table 2
EIS fitted parameters of the porous NieCu alloy electrode at different potentials.

Overpotential
0.25 V
0.28 V
0.30 V
0.32 V
0.35 V

Rs (U cm
2) 0.06 0.067 0.067 0.066 0.066

CPE-1(F cm
2) 1.32  10
3 1.32  10
3 9.38  10
4 6.16  10
4 1.05  10
4
n1 1 1 1 1 1
R1(U cm
2) 5.21 4.18 3.42 5.122 4.20
CPE-2(F cm
2) 4.72  10
3 4.03  10
3 3.53  10
3 2.17  10
3 4.15  10
4
n2 0.97 0.97 0.98 0.98 0.99
R2(U cm
2) 124.2 57.09 16.46 3.82 0.69

reaction has also been reported on other porous materials
[35,37,38], which may be caused by the diffusional limiting process
with respect to the complex and irregular porous structures [31,35].
The product of gas bubbles is an additional impediment which
contributes to the concentration polarization and ohmic resistance
inside the pores [35]. Mathematical models also predict the in-
crease or even doubling of the Tafel slope for porous materials
during the HER process [39].
3.2.3. EIS test of porous NieCu alloy cathode
Electrochemical impedance spectroscopy (EIS) is a very sensi-
tive technique for understanding the electrode reactions on porous
electrodes [40]. The representative Nyquist plots of the porous
(a)
348K
0.0
338K
Current density (A/cm2)
NieCu electrode at different overpotentials near the hydrogen
evolution region are presented in Fig. 4a; phase angle-frequency
plots for the same system are shown in Fig. 4b. Hollow symbols
represent experimental points, while solid lines represent fitting
results.
It can be seen from Fig. 4a that the EIS behavior of porous NieCu
is dependent on the electrolysis potential. As the overpotential
increase, the diameter of the semicircle observed in the Nyquist
plots decreases. The equivalent circuit for modeling the electro-
chemical impedance data is presented as inset in Fig. 4a. The EIS
data obtained at different potentials are well fitted by 2-CPE model
[41], predicting the formation of two partially overlapped semi-
circles, with the HF (high frequency) semicircle related to the
porous structure of electrodes and the LF (low frequency) semi-
circle to the faradic process [42]. Two peaks are observed in the
phase angle-frequency plots corresponding to the two semicircles
appearing in Nyquist plots. However, the peak at LF is gradually not
distinguishable as the overpotential increases, which makes a
deformed semicircle in the Nyquist plot. The deformed semicircle

328K appears at high overpotential in the impedance spectra has also

318K
-0.1 been reported on skeleton NiTi [11], Raney-nickel composite coated
308K electrodes [43,44].
348K
0.0 348K 338K
328K
Table 2 reports the corresponding parameter values obtained
-0.2 -0.1 318K
308K
from the experimental impedance data fitted on porous NieCu at
η (V)

-0.2
different overpotentials. Where Rs is solution resistance; CPE
(constant phase element) is related to the double-layer capacity of
-0.3 -0.3
308K the electrodes; R1 and R2 are related to the porous structure and the
-0.4 kinetics of the Faradaic reaction of the HER, respectively. As it is
-1.4 -1.2 -1.0 -0.8
seen from Table 2, R1 value almost remains constant, and the CPE-1
-0.4 Log i/Acm-2 behaves as ideal capacitor; however, both CPE-2 and R2 value
-1.8 -1.6 -1.4 -1.2 -1.0 decrease with increasing overpotential. The decreased CPE-2 is
most likely due to the blockage of adsorbed hydrogen on the sur-
Potential/V (vs.SCE) face [24]. The low charge transfer resistance R2 at high potential is
(b) -1 in accordance with the observed high exchange current density for
HER. The values of time dependent parameter n are approximately
Dense Ni equal to 1.0 indicating a homogenous surface of the porous
-2 Porous Ni-Cu electrodes.
It is generally accepted that the HER on transition metals in
alkaline solution goes through the usual Volmer-Heyrovsky
-3
Logi/Acm-2

mechanism [45]. It can be written as:

-4 H2O þ M þ e
/ M-Hads þ OH
(I) Volmer step

M-Hads þ H2O þ e
/ M þ H2 þ OH
(II) Heyrovsky step

-5
Where M is a free site on the metal surface and MHads is the
-6 metal surface occupied by hydrogen adatoms. It can be derived

0.0029 0.0030 0.0031 0.0032 0.0033 Table 3

The calculated apparent activation energy for porous NieCu alloy and dense Ni.
1/T (K-1)
Electrodes NieMoeCu Dense Ni Porous NieCu
Fig. 5. (a) The catalytic activity of porous NieCu alloy for HER at different tempera-
Apparent activation 21.0 44.1 26.7
tures (with inset figure of Tafel linear region); (b) Arrhenius plot of porous NieCu alloy
energy(kJ mol
1) (reference)
and dense Ni.
 L. Yu et al. / Energy 97 (2016) 498e505 503

(a) from the EIS study that, as the overpotential increases, the low
frequency semicircle in the impedance plots becomes smaller and
0.00 100st smaller, indicating that the adsorption process is promoted and the
200st charge transfer process dominates the impedance response as the
Current density (A/cm2)

300st overpotential increases [46]. Hence, the hydrogen evolution reac-

-0.04 400st tion on porous NieCu alloy is controlled by Heyrovsky step.

Current density (A/cm2)

500st -0.110
-0.08
3.3. The effect of temperature on the electro-catalysis activity of
-0.115
cathodes
-0.12
-0.120 For this study, the cathode polarization curves on porous NieCu
at temperatures ranging from 35  C to 75  C are recorded. Linear
-0.16 -0.125 regions of Tafel plots at different temperatures are demonstrated in
-1.720 -1.715
Potential/V (vs. SCE) the inset of Fig. 5a. As temperature increases, the overpotential
-0.20 evidently decreases at the same current density, and the onset
-2.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 potential of HER shifts to positive direction. The exchange current
density is extrapolated from Tafel plot according to equation (2),
Potential/V (vs.SCE)
and the relationship between j0 and T for HER is exhibited in Fig. 5b.
It is shown that the increase of temperature promotes the HER
activity of both porous NieCu and dense Ni. The curve of log j0
(b) against T
1 exhibits a linear relationship in Fig. 5b. Substituting the
0.00 100st slope value into Arrhenius equation (3) [47], the apparent activa-
200st tion energies (Ea) for HER of two electrodes are obtained and
Current density (A/cm2)

300st presented in Table 3.

-0.01 400st
-0.015 Ea
500st log j0 ¼ log A
1
Current density (A/cm2)

(3)
2:303R =T
-0.020
-0.02
The calculated value of apparent activation energy for the
-0.025
porous NieCu is 26.7 kJ mol
1, lower than that of dense Ni
-0.03 -0.030 (44.1 kJ mol
1), dense NieCu (32.6 kJ mol
1), and reported porous
-0.035
Ni3Al (30.1 kJ mol
1) [30], NieFe (31 kJ mol
1) [48], and comparable
to that of electrodeposited NieMo alloy [49]. It indicates a lower
-0.040
-0.04 -1.75 -1.70 -1.65 energy barrier of HER on the porous NieCu electrode in alkaline
Potential/V (vs.SCE) solution. This result further proves the high electroecatalytic ac-
-2.0 -1.8 -1.6 -1.4 -1.2 -1.0 tivity of the sintered porous NieCu from the viewpoint of dy-
namics. However, the value of Ea is still higher than ternary
Potential/V (vs.SCE) NieMoeCu (21 kJ mol
1) [50] cathode for HER at the same elec-
trolysis condition, which prompts that the addition of active
Fig. 6. Cyclic voltammograms in 6.0 M KOH at the scan rate of 1 mV s
1 for 500 cycles
on: (a) porous NieCu alloy; (b) dense Ni. component Mo to the porous NieCu alloy may help decrease the
apparent activation energy during HER.

Fig. 7. SEM micrograph and EDS analysis of porous NieCu cathode running after 500 cycles of CV test.
504 L. Yu et al. / Energy 97 (2016) 498e505

3.4. The electrochemical stability of porous NieCu alloy cathode as cathode for the HER was studied by cathodic polarization curves,
EIS and CV techniques. An increase in electrocatalytic activity was
The electrochemical stability of electrode is investigated by observed for the porous NieCu alloy electrode compared with
recording CV curves in 6.0 M KOH at the region of
0.9 to
1.8 V at dense nickel, due to the enlarged active surface area and the
298 K at the scanning rate of 1 mV s
1 for 500 cycles. As shown in increased intrinsic catalytic activity after introducing Cu into Ni.
Fig. 6, there is only 3.3% current decay for porous NieCu yet a 38.0%
current decay as for dense Ni after 500 cycles CV tests. The surface
morphology of porous NieCu after test is shown in Fig. 7a, which (a)1000
shows the skeleton still in its original state. From energy spectrum
(Fig. 7b) analysis, no adhering impurity exists on the surface of the
cathode material, reflecting that the current interruption has no 5h
800 -44.2o
impact on the alloy electrode's catalytic activity and surface 36h
morphology. For the electrodes obtained by electro-deposition,
previous studies show that electro-deposited coating will be 600

Z" (ohm)
peeled off from substrate during short running cycles because of the
entrance of hydrogen, causing permanent destruction of electrodes -59.3o
[51]. However, the interconnected pores of the porous NieCu make 400
the hydrogen escape smoothly from the pore channels, retaining the
integrity of the porous skeleton. Under this consideration, opti-
mizing average diameter of the pore channels, as well as increasing 200 -29.5o
actual surface of the porous structure of the sintered NieCu for HER -51.8o
application will be one subject of our further researches. 0
The characteristic of net-shape forming by powder metallurgy
provides advantages such as structure stability and easy manufac- 0 200 400 600 800 1000
ture of materials, which can seldom be obtained by other tech-
Z' (ohm)
niques for electrode fabrication. Meanwhile, the inherent
characteristics of metal ensure excellent strength of the porous
NieCu, with the transverse rupture strength and tensile strength at
(b)
70
room temperature 140.5 MPa and 73.1 MPa, respectively. Sufficient
strength of the material can afford more severe operating condition 60
during the hydrogen produce by water electrolysis.
50
-Phase (degree)

3.5. The corrosion resistance of porous NieCu alloy in KOH solution

40
Although a promising electrocatalytical performance is 5h
30
observed for porous NieCu cathode, it remains to be seen if this
36h
material will have sufficient resilience to chemical attack by the
caustic solution over long period of service. 20
The Nyquist and Bode plots are given in Fig. 8a and b for the
porous NieCu cathode in 6.0 M KOH solution at 25  C after 5 and
10
36 h of exposure (at open circuit conditions). Two time constants
0 -2
can be seen from the Bode plots, corresponding to the two capac- 10 10
-1
10
0
10
1
10
2 3
10
4
10
itive loops in the Nyquist plots. The appearance of the first loop at
high frequencies is related to the porous structure, which is inde- Frequency (Hz)
pendent on the exposure time. The second capacitive loop is
attributed to the charge transfer resistance, which corresponds to (c) -0.16
metal dissolution process, indicating that the corrosion reaction of
the electrode is charge transfer controlled. The polarization re-
sistances of the porous NieCu electrode in 6.0 M KOH solution are -0.20
PotentialOCP/V (vs.SCE)

also determined and found to be 1080 and 2240 U cm
2 after 5 and
36 h of exposure, respectively. The increasing corrosion resistance
with exposure time may be related to the growth of protective -0.24
oxide and/or hydroxide products of nickel (NiO, Ni(OH)2, NiOOH)
and copper (Cu2O, CuO, Cu(OH)2) [22,52,53] during immersion. -0.28
The variation of the open circuit potential (Eocp) with time for
porous NieCu as long as 60 h is recorded in Fig. 8c, parallel experi-
ments show the same feature of change. The Eocp values of the porous -0.32
NieCu electrode are
0.32 and
0.19 V after 5 and 36 h of exposure,
respectively. The positive variation of open circuit potential is due to
-0.36
the formation of a passive oxide layer over the electrode surface. 0 10 20 30 40 50 60

4. Conclusions Immersion time (hours)

Fig. 8. The Nyquist (a) and Bode (b) plots of porous NieCu cathode obtained after 5 h
The porous NieCu alloy with an open porosity of 31.5% was and 36 h immersion times in 6.0 M KOH solution; The Eocp variation of porous NieCu
fabricated by powder metallurgy, and its activity as well as stability alloy with immersion time (c).
 L. Yu et al. / Energy 97 (2016) 498e505
Furthermore, it is demonstrated that the sintered porous NieCu
alloy cathode has excellent stability during HER, almost completely
retaining its current density, even after 500 cycles. The excellent
electrocatalytic and chemical stability make the fabricated porous
NieCu material a potential compound as cathode in alkaline water
electrolysis.
Present research encourages more efforts to study the porous
NieCu binary alloy system for HER, the effect of alloy composition
on the strength of M-Hads, as well as the influence of pore structure
of the sintered porous NieCu material on the hydrogen production
by water electrolysis.
Acknowledgements
This research was financially supported by the State science and
technology support program (2012BAC02B05).
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