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 ) 1 7 0 1 e1 7 0 9

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3D nickel foams with controlled morphologies for

hydrogen evolution reaction in highly alkaline
media

K.I. Siwek a,*, S. Eug
enio a,b,**, D.M.F. Santos c, M.T. Silva a,d,
M.F. Montemor a
a
Centro de Quı́mica Estrutural (CQE), Instituto Superior T
ecnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal
b
^ntica e School of Management Sciences, Health, IT & Engineering, Fa
Atla
brica da P
olvora de Barcarena, 2730-036
Barcarena, Portugal
c
Center of Physics and Engineering of Advanced Materials (CeFEMA), Instituto Superior T
ecnico, Universidade de
Lisboa, 1049-001 Lisbon, Portugal
d
Department of Mechanical Engineering, GI-MOSM, Instituto Superior de Engenharia de Lisboa, 1950-062 Lisbon,
Portugal

article info abstract

Article history: Water electrolysis is the cleanest method for hydrogen production, and can be 100% green
Received 12 September 2018 when renewable energy is used as electricity source. When the hydrogen evolution reaction
Received in revised form (HER) is carried out in alkaline media, nickel (Ni) is a low cost catalyst and an interesting
21 October 2018 alternative to platinum. Still, its performance has to be enhanced to meet the high efficiency
Accepted 11 November 2018 of the nobler metals, an objective that requires further tailoring of the surface area and
Available online 6 December 2018 morphology of Ni-based electrode materials. Unlike commercially available porous Ni, these
features can be easily controlled via electrodeposition, a one-step process, taking advantage
Keywords: of the dynamic hydrogen bubble template (DHBT). Generally, changes in surface porosity and
3D nickel foams morphology have been mainly achieved by altering the main parameters, such as the current
Electrodeposition density or the deposition time. However, very scarce work has been done on the role of
Morphology supporting electrolyte (i.e., its concentration and composition) in tailoring the foam features
Hydrogen evolution reaction and consequently their catalytic activity. Hence, this approach paves the way to optimum
design of metallic foam structures that can be obtained only with modifications in the
electrolytic bath. In this work, 3D Ni foams are obtained from different composition baths by
galvanostatic electrodeposition in the hydrogen evolution regime on stainless steel current
collectors. Their porosity and morphology are analysed by optical microscopy and SEM. The
electrochemical performance is evaluated by cyclic voltammetry, while catalytic activity
towards HER and materials’ stability in 8 M KOH are tested using polarisation curves and
chronoamperometry measurements, respectively. The recorded high currents and extended
stability of the Ni foams with dendritic morphology demonstrate its outstanding perfor-
mance, making it an attractive cathode material for HER in highly alkaline media.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
** Corresponding author. Atla^ ntica e School of Management Sciences, Health, IT & Engineering, Fa

brica da Po

lvora de Barcarena, 2730-
036 Barcarena, Portugal
E-mail addresses: katarzyna.siwek@tecnico.ulisboa.pt (K.I. Siwek), s.eugenio@tecnico.ulisboa.pt (S. Euge
nio).
https://doi.org/10.1016/j.ijhydene.2018.11.070
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
1702 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 ) 1 7 0 1 e1 7 0 9
Introduction
Hydrogen is one of the most promising fuels for the future, as
we move towards a sustainable, fossil fuel-free society [1].
However, to meet the current energy and economics demand,
hydrogen production processes still require significant im-
provements. Alkaline water electrolysis is an environmentally
friendly method to produce high-purity hydrogen gas, but its
widespread commercial application is hindered by the low
efficiency of the process [2]. One of the strategies for mini-
mising this disadvantage is the optimisation of the electrode
materials of the electrolyser, which will result in lower elec-
trode overpotentials, increased chemical stability and elec-
trocatalytic activity, while maintaining a low cost [3].
Among electrode materials, platinum (Pt) is known to be
highly active for the hydrogen evolution reaction (HER) but its
high price and relative scarcity limit its commercial application
[3]. Nickel (Ni) is considered a lower-cost non-noble metal
alternative to Pt but despite extensive research [2e19] its per-
formance for HER still needs to be enhanced. Besides the na-
ture of the material, high surface area and tailored morphology
are also important features of catalytic materials. Porosity en-
sures an economical use of the material and improves the
accessibility of reactants, while the presence of fine nano-
structures influences the electrocatalytic activity for HER
[7e11]. Several methods can be used to obtain high surface area
metallic catalysts, such as spraying or magnetic sputtering [12],
chemical vapour deposition [13], electrodeposition [7,9,11] and
alkaline leaching of aluminium from NieAl Raney nickel
[2,14,15,20,21]. However, the former two are multi-step pro-
cesses, with a low deposition rate and a relatively high cost,
while the latter faces issues of controlling the pore size, relative
density and reproducibility. As a promising alternative, the
preparation of porous materials using the dynamic hydrogen
bubble template (DHBT) has been proposed [16e18,22]. Marozzi
and Chialvo [16] were one of the first to study the development
of pure porous Ni deposits and showed that the application of
high current densities could lead to macroporous structures
with different morphologies. The reported electrodes, despite
having lower surface roughness than commonly used Raney
nickel (pore diameter < 10 nm), possess higher accessible sur-
face area, that could be efficiently used during the process [16].
In this one-step method, electrodeposition is carried out under
intense hydrogen bubble evolution, forming a dynamic tem-
plate that results in a highly porous deposit. The size of the
pores or holes is related to the size of the evolving hydrogen
bubbles, whereas the morphology, which can range from
dendritic to cauliflower-like, depends on the nucleation and
growth mechanism of the metal, changing with the hydrody-
namic conditions during deposition [23]. Hence, the film can be
tailored by tuning the applied current density and deposition
time. The electrolyte concentration and composition affect the
mechanical stability of the deposit [23] nevertheless, studies
done on copper [24] showed that morphology control can also
be achieved by adding shape directing agents to the electrolyte
(e.g., NaCl). Therefore, considering the role of fine nano-
structures in the electrode activity towards HER, it is important
to explore electrolyte composition as a way of tuning the
overall film morphology.
In this work, 3D Ni foams were deposited onto stainless
steel via galvanostatic deposition from different electrolytes.
The effect of electrolyte composition on both surface micro-
size pores and deposit morphology and, consequently on the
foams’ activity towards HER and overall stability in strongly
alkaline media, was studied and discussed. The surface of the
3D Ni foams was analysed by optical microscopy and scanning
electron microscopy, while its electrochemical performance in
alkaline media was evaluated using cyclic voltammetry, linear
scan voltammetry and chronoamperometry measurements.
Experimental
Synthesis of the 3D Ni foams
Ni foams were cathodically electrodeposited from three
different chloride-based solutions, (Table 1). NiCl2.6H2O
(Sigma-Aldrich, 98 wt%), NH4Cl (Sigma-Aldrich, 99.5 wt.%) and
NaCl (Panreac, 99 wt.%) were used as received without further
purification. The deposition process was carried out in a 2-
electrode cell (75 mL volume) connected to a power source
(Sorensen LH110). A graphite plate was used as counter elec-
trode and a stainless steel plate (AISI 304, Goodfellow) with an
active area of 1.65 cm2 was employed as the working elec-
trode. Prior to deposition, the steel substrate was polished
with 600 SiC grit paper, cleaned with acetone in ultrasound
and dried with an air jet. All foams were deposited by applying
a current density of
1 A cm
2 for 150 s. Then, they were
thoroughly rinsed with distilled water to remove the
remaining electrolyte and dried with an air jet. The
morphology and porosity of the deposited foams were char-
acterised by scanning electron microscopy (SEM, JEOL 7001-F)
and optical microscopy (Leica DMS300). X-ray diffraction
(XRD) was performed using a Bruker AXS D8 Advance instru-
ment with Cu Ka radiation (1.5418  A). The diffractograms were
acquired between 10 and 80 with a step size of 0.02 and a
step time of 10 s.
Electrochemical measurements
Cyclic voltammetry (CV), linear scan voltammetry (LSV) and
chronoamperometry (CA) were conducted using a VoltaLab
PGZ 100 potentiostat/galvanostat in a 75 mL electrochemical
cell with a conventional three-electrode arrangement. Each of
the three different foams was employed as the working elec-
trode, Pt coil served as counter electrode and Hg/HgO elec-
trode (8 M KOH, Gamry 5088) as reference. All potentials given
Table 1 e Electrolyte composition and corresponding pH
used for electrodeposition of Ni foams with given mass.
Sample Electrolyte composition Bath pH Foam
mass/mg
Foam 1 0.1 M NiCl2$6H2O þ 3.50 15.1
2 M NH4Cl
Foam 2 0.1 M NiCl2$6H2O þ 3.83 16.54
1 M NH4Cl þ 1 M NaCl
Foam 3 0.1 M NiCl2$6H2O þ 1 M NH4Cl 4.02 18.21
 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 ) 1 7 0 1 e1 7 0 9 1703

in the paper were converted to reversible hydrogen electrode

(RHE) reference scale using the formula ERHE ¼ EHg/
HgO þ 1.015 V (Fig. S1 in Electronic Supplementary Informa-
tion, ESI). The foams geometric area was 1 cm2 and this value
was used for calculation of the current densities throughout
the paper. The HER electrocatalytic activity of prepared Ni
foams was directly compared to that of a commercially
available Ni rod (Goodfellow, A ¼ 1.13 cm2). All measurements
were conducted in 8 M KOH (Sigma-Aldrich, 90 wt%) solution,
typically used in industrial alkaline water electrolysis (ca.
30 wt% KOH). Prior to the measurements, all foams were
subjected to a constant potential of
0.065 V for 25 min to
ensure the complete removal of surface oxides. LSV was then
used to scan the electrode potential from its open circuit po-
tential (OCP) down to
0.30 V at a scan rate of 0.5 mV s
1.
Chronoamperometry at fixed potential of
0.35 V (IR uncor-
rected) was further used to assess the stability of the mate-
rials. In order to evaluate the morphology/porosity effect on
the electrochemical performance, the foams were cycled be-
tween 1.01 and 1.71 V at scan rates in the 5e80 mV s
1 range.
The foams electrochemically active surface areas were esti-
mated using double layer capacitance calculations.
Result and discussion
Characterisation of the 3D Ni foams
All the Ni deposits obtained in the present study present a
foam-like structure with 3D porous architecture (Fig. 1). It was
clear that the NH4Cl concentration and the presence of NaCl in
the electrolyte influenced both the porosity and morphology
of the foams. As can be seen in Fig. 1aef, foam 1 shows higher
surface porosity and lower pore-size distribution compared to
foams 2 and 3. This indicates a decrease in the micro-size
pores density with decreasing concentration of NH4Cl in the
electrolyte, in agreement with previous reports [16,23,25].
Additionally, the morphology of the deposit changed from
cauliflower-like to dendritic when the concentration of NH4Cl
decreased from 2 M (foam 1) to 1 M (foams 2 and 3) (Fig. 1gei).
The dendrites in foam 2, obtained with lower concentrations
of NH4Cl in the presence of NaCl revealed a flower-like
structure (Fig. 1h). In the absence of NaCl, the dendrites
maintain the flower-like structure but backbone particles
connecting the tips of the dendrites are commonly observed

Fig. 1 e a-c) Optical micrographs of foams' surfaces taken at magnification of £ 20 and SEM images of the top view of the
corresponding foams surface at different magnifications, d-f) £ 1000 and g-i) £ 10000. The insets in Fig. 1g and h shows a
cauliflower and a flower, respectively.
1704 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 ) 1 7 0 1 e1 7 0 9
(Fig. 1i). These morphological variations can indeed result
from the presence of NaCl, which has been reported as a
shape directing and texture-improving agent [24]. A recent
study [26] showed that NaCl is absorbed into certain crystal
facets during the structure growth, altering the path of its
further development from an outer edge direction to a more
vertical one. In this sense, the growth of horizontal backbone
particles, observed on the surface of foam 3, is inhibited in the
presence of NaCl. This was confirmed in XRD patterns pre-
sented in Fig. 2, where three diffractions facets (111), (200) and
(220), typically observed for faced centred cubic Ni were
recorded. However, when NaCl was added to the electrolyte
(foam 2), the peaks intensity of Ni (111) and (200) increased,
which may suggest its influence on crystal planes. Moreover,
NaCl addition improves electrolyte conductivity, thus mini-
mising the iR drop. This causes the rate of deposition to be
uniform throughout the growing deposit, generating a less
defected surface [27]. This effect may also explain the absence
of cracks on the surface of foams 1 and 2 (Fig. 1a and b), where
the total ions concentration in the bath was 2 times higher
than in the case of foam 3 (Fig. 1c).
The foam-like morphology of the deposits is, to some
extent, determined by the amount of evolved hydrogen bub-
bles [28]. During electrodeposition at pH < 6.75 (higher pH fa-
vours precipitation of nickel hydroxide) and under intense
hydrogen (H2) evolution, the metal will discharge from the
free ions (Eq. (1)) [25] and grow in the space between the
continuously evolving bubbles (generated through mecha-
nism 2a followed by 2b or 2c and through Eq. (3)) [22]:
NiðaqÞ þ 2e
/NiðsÞ
2þ
Hþ
NH4Cl in the formation of 3D structures is attributed to the
ðaqÞ þ e /HðadsÞ
Hþ

ðaqÞ þ HðadsÞ þ e / H2
2HðadsÞ /H2
Fig. 2 e XRD patterns of Ni foams obtained from different
electrolyte bath composition.
2NHþ

4 þ 2e /H2 þ 2NH3 (3)
Hence, the bubbles act as negative template, forming
micro-size pores as they detach from the electrode surface.
Pore distribution and wall morphology can therefore be
controlled by altering the process conditions, including con-
centration of electrolyte species. The increase in NH4Cl con-
centration, as both bubble stabiliser and a source of H3Oþ ions
(Eq. (3)), will have a direct impact on hydrogen bubble evolu-
tion [23]. Hence, leading to increased surface porosity as well
as micro-size pores density and changes of the hydrodynamic
conditions in the electrode layer [25,28]. This might explain
the differences between the morphologies observed in the
deposits obtained from electrolytes with lower and higher
concentration of NH4Cl. At high NH4Cl concentration (elec-
trolyte for the deposition of foam 1), bubbles coalescence is
hindered, providing more intense hydrogen evolution (more
bubbles with smaller diameter participate in the process). This
effect decreases the Ni reduction overpotentials by disturbing
the diffusion layer thickness and therefore resulting in
compact morphological features, typically obtained at lower
deposition potential (nucleation theory of metal electrodepo-
sition) [28,29]. In other words, thinner diffusion layer in-
creases the limiting current density and promotes faster
build-up of double layer, which is demonstrated by a poten-
tial drop in galvanostatic regime. Interestingly, at lower NH4Cl
concentration more dendritic-like morphologies were
observed for foams 2 and 3, suggesting that diffusion layer
thickness was not sufficiently disturbed by evolved hydrogen
(1) due to prolonged detachment time of coalescent bubbles. In
general, and in agreement with the literature, the role of
(2a)
increase of hydrogen evolution rate with increasing NH4Cl
concentration [16,25].
(2b)
Cyclic voltammetry studies
(2c)
To better understand the effect of discussed morphology and
porosity on the foams electrochemical behaviour in 8 M KOH,
cyclic voltammetry (CV) was performed at various scan rates
(Fig. S2a,c and e in ESI). The CVs of the foams and the Ni rod
electrode obtained with selected scan rates, n, of 10 and
30 mV s
1 are shown in Fig. 3. The typical CV of a Ni electrode
in alkaline media is characterised by well-defined anodic and
cathodic peaks, which correspond to the redox reaction
described by Eq. (4) [30,31].
NiðOHÞ2 þ OH
4NiOOH þ H2 O þ e
(4)
These redox peaks are clearly visible in Fig. 3, with those of
the Ni foams being more intense, clearly separated and
broader than those of the Ni rod. The difference in shape and
peak-to-peak separation (DEp, defined as the potential differ-
ence between the oxidation Eox, and reduction, Ered, peaks)
can be related to electrolyte diffusion limitations (irrevers-
ibility of redox reaction, DEp > 57 mV), being more pronounced
inside the thick porous network, while increase in current
densities is attributed to the foams enhanced surface area. In
case of porous deposits, DEp increases with n, in agreement
with the literature [32,33]. Low n values allow for a longer
 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 ) 1 7 0 1 e1 7 0 9 1705

case equal to the electrochemically active surface area,

ECSA), were estimated according to the relation expressed by
Eq. (5) [35].

ECSA
Rf ¼ ¼ ECSA (5)
Ageometric¼1

ECSA is determined as the ratio of the double layer

capacitance for the foam, Cdl foam, and that for smooth Ni rod,
Cdl Ni smooth. Value of 20 mm cm
2 is considered for an ideally
smooth Ni electrode prepared by chemical methods, as
commonly referred in the literature [7e9]. The linear slope of
the average capacitive current, jdl, as a function of the scan
rate, n (Fig. 4), allows assessing the double layer capacitance,
Cdl, according to the expression in Eq. (6),
     
 jc  þ  ja  dE
jdl ¼ ¼ Cdl (6)
2 dt

where jc and ja stand for the cathodic and anodic current

densities, respectively.
The results collected in Table 2 indicate the increase in Rf
(in regards to the higher value of Cdl) and, consequently, in the
ECSA, in the following order: foam 1 < foam 2 < foam 3. This
confirms the suggested relation (at higher n) between DEp and
ECSA, and additionally explains the increase in current den-
sity, being the lowest for foam 1 and the highest for foam 3,
even after current density normalisation to the foams mass
(Fig. S3 in ESI). The substantial increase in ECSA of foam 3 can
be related to distinct surface heterogeneity, lower pore dis-
tribution (higher pores density and larger pore size compro-
mise surface area) as well as higher deposited mass when
compared to foams 2 and 1.

Fig. 3 e Cyclic voltammograms obtained for Ni rod (inset)

and for the three Ni foams in 8 M KOH solution at scan rate
of a) 10 mV s¡1 and b) 30 mV s¡1.

reaction time that leads to more electroactive species being

consumed, while at higher n reactions are accelerated, leading
to a shorter time for electrolyte replenishment inside of the
pores and, consequently, to greater DEp values [33]. Interest-
ingly, when the foams are scanned at 10 mV s
1 peaks sepa-
ration for each of the foam remained identical (140 mV),
despite the shift in Eox for foam 1 (25 mV) to more positive
values when compared to foams 2 and 3. In addition, Eox of
foam 1 showed more regular shape than in the case of the two
Fig. 4 e Charging current density differences plotted as a
other foams. These remarks may be the consequence of
function of the potential scan rate.
higher porosity as well as morphological features of foam 1.
However, when n was increased to 30 mV s
1, DEp changed to
230, 280 and 320 mV for foams 1, 2 and 3 respectively. This is
Table 2 e Double layer capacitance and roughness factors
most likely related to the ohmic drop within the thick films, at
measured for the three Ni foams.
higher n, that differ depending on the surface area, which in
Cdl/uF cm
2 Rf (Cdl foam/Cdl Ni smooth)
turn depends on particle and pore size distribution [34].
To confirm it, double layer regions (Fig. S2b,d and f in ESI) Foam 1 6300 315
were selected for each sample (taking into account the in- Foam 2 9700 485
Foam 3 12700 635
fluence of scan rate on DEp) and roughness factors, Rf (in this
1706 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 ) 1 7 0 1 e1 7 0 9
Hydrogen evolution reaction studies
The activity of both Ni foams and Ni rod electrode for HER was
studied in 8 M KOH at room temperature using linear scan
voltammetry (LSV). Fig. 5a shows the polarisation curves ob-
tained by scanning the foam electrode potential from the OCP
(Table 3) until
0.3 V at scan rate of 0.5 mV s
1. Based on the
polarisation curves, the corresponding Tafel plots can be ob-
tained (Fig. 5b). The HER kinetic parameters may then be
determined (Table 3) from the Tafel plots and by application of
Eqs. (7)e(9),
h ¼ a þ b log j
2:3 RT
b¼
aF
a activity to HER. Among porous Ni, foams 2 and 3 revealed the
j0 ¼ 10
b
where the overpotential, h, is the difference between the OCP
and the applied potential, a is the intercept related to the
Fig. 5 e a) Linear polarisation curves of Ni foams and Ni rod
and b) the corresponding Tafel plots.
Table 3 e Kinetic parameters calculated from the Tafel
plots for the four Ni-based electrodes.
b/mV a j0/mA cm
2 jECSA
0 /mA cm
2 ƞonset/mV
dec
1
Foam 1
100 0.59 2.57  10
2 8.15  10
5 190
Foam 2
105 0.56 6.53  10
2 1.34  10
4 150
Foam 3
160 0.36 6.31  10
1 9.92  10
4 130
Ni rod
98 0.60 8.98  10
4 8.98  10
4 210
exchange current density, j0, which defines the reaction rate, b is
the Tafel slope, which reflects the change of j with h, T is the
(7)
temperature in Kelvin, R and F indicate the ideal gas constant
(8.314 J mol
1 K
1) and Faraday's constant (96485C mol
1),
(8) respectively. The obtained Tafel plots (Fig. 5b) and the correlated
kinetic parameters (Table 3) displayed differences for the foams
(9)
lowest onset overpotential, ƞonset, for HER, starting at 150 and
130 mV respectively, followed by foam 1, with ƞonset starting at
190 mV and Ni rod at 210 mV. The decrease in ƞonset is accom-
panied by an increase in j0, which is proportional to the ECSA.
For this reason, j0 was normalised to the estimated ECSA values
(Table 2), which is generally omitted in most studies regarding
porous electrodes. It is evident that an increase in ECSA pro-
duces an enhanced electrode performance, in agreement with
literature [3]. In fact, j0 of foam 3 is one of the highest reported so
far for Ni-based electrodes, considering both the geometric and
the real surface area [3e5,7,8,37]. Further analysis of the elec-
trodes activity for HER was based on the determined Tafel slope,
which gives an insight into the reaction kinetics.
The HER may be described by two possible mechanisms [3],
which always include the initial hydrogen adsorption (Volmer
step) followed either by electrochemical desorption (Heyr-
ovsky step) or chemical recombination (Tafel step). When
each one of these steps is the HER rate-determining step, it
yields a Tafel slope of 120, 40 and 30 mV dec
1, respectively.
However, if HER is occurring on a porous matrix (e.g., Raney
Ni), deviations to the latter values are commonly observed,
due to the complexity of the electrode structure. It has been
reported [2] that Raney Ni electrodes lead to an intermediate
slope between 40 and 120 mV dec
1, predicted for the
VolmereHeyrovsky reaction mechanism. This range covers
the values of Tafel slope found for foam 1 and foam 2, but not
for foam 3 (Table 3). Higher Tafel slope values have already
been reported for other porous materials [3,21,36,37].
Stability measurements
In addition to evaluating the catalytic activity, the stability is
also an important criterion to assess the performance of Ni-
based electrodes for HER. Therefore, chronoamperometry
(CA) was used to perform durability tests. The measurements
were conducted at constant applied potential of
0.35 V. The
current transients recorded at 25  C are depicted in Fig. 6a. The
catalytic currents increased in the following order: Ni
rod < foam 1 < foam 2 < foam 3. It is interesting to notice that
the current difference between foam 2 and foam 3 is much
lower (18 mA cm
2) than that between foam 1 and foam 2
(44 mA cm
2), despite the similar ratios of real surface areas
(ECSAfoam3/ECSAfoam2 ¼ 1.3 and ECSAfoam2/ECSAfoam1 ¼ 1.5).
 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 ) 1 7 0 1 e1 7 0 9
Fig. 6 e a) Chronoamperometry measurements of Ni foams
and Ni rod obtained at ¡0.35 V and b) the corresponding
current retention related to current at time ¼ 0.4.
Another remarkable observation is related to the fast decay of
current density to 70 and 80% of the initial value during the
first 100 s recorded for the Ni rod and for foam 1, respectively
(Fig. 6b). However, in case of Ni rod, the current drop pro-
gressed with time reaching 25% of its initial value after 4h,
while foam 1 stabilised within 1.5 h of test retaining 68% of the
initial current. Conversely, only small decrease (3e5%) was
measured for foams 2 and 3 (Fig. 6b). The source of decrease in
electrode performance may be attributed to nickel hydride
formation, a well-known phenomenon [38e40]. Many authors
have pointed out their effect on Ni activity; however, there is
no consistency in the obtained results. Hydrides formation
works analogously to oxides formation, but in a cathodic
regime. It has been suggested [40], that in concentrated elec-
trolyte and at high overpotentials, hydrogen can be incorpo-
rated rapidly into material along grain boundaries and
dislocation defect decreasing the density of electronic state
value at Fermi level, which results in lower number of avail-
able electrons and consequently lower activity. This might be
the case of the behaviour observed for the smooth Ni rod and
1707
for foam 1. However, Ni rod showed continuous decrease in
current density throughout the whole measurement time,
while foam 1 stabilised after a certain period (Fig. 6). In gen-
eral, hydride formation has been shown to depend on crystal
arrangement, atomic size and number of valence electrons
[38], thus may differ on different surfaces as well.
However, it is important to point out, that the loss of per-
formance Foam 3 < Foam 2 < Foam 1 < Ni rod is consistent
with decreasing surface area. It suggests that, under the same
conditions, the material with lower surface area is more sus-
ceptible to this phenomenon, possibly due to higher rate of
hydrogen adsorption and faster formation of nickel hydrates.
On the other hand, this explanation does not satisfy the
observed behaviour of foam 1. Further research is needed to
determine the role of surface area and certain morphology in
the electrode deactivation. In some way, the dendritic struc-
tures of foams 2 and 3 were not subjected to performance loss
making them a suitable morphology for 3D electrodes used for
alkaline water electrolysis.
Conclusions
Porous 3D Ni metallic foams produced by electrodeposition
using the dynamic hydrogen bubble template presented sig-
nificant differences in terms of structure, surface morphology
and activity toward HER, depending on the deposition bath
electrolyte composition. An increasing concentration of
hydrogen ions in the electrolyte lead to the formation of foams
with a cauliflower-like morphology and high pores density
(foam 1). The addition of NaCl to the electrolyte with lower
concentration of NH4Cl (foam 2) increased the electrolyte
conductivity and induced the directional growth of dendritic
structures. The structural heterogeneity increased with
decreasing total ion concentration (<2 M) in the bath (foam 3).
Foams 2 and 3 presented larger electroactive surface areas,
possibly due to presence of dendritic architectures, previously
reported to favour the electrochemical surface utilisation. In
all cases, the development of a porous structure increased
significantly the HER current densities compared to the Ni rod
electrode. Further calculation of most relevant kinetic pa-
rameters and stability measurements confirmed superior HER
performance of dendritic morphology over cauliflower one
regarding higher generated currents and lower onset over-
potential. The results suggest that the foams morphology, as
well as porosity, plays an important role in the determination
of the catalytic efficiency of the material and can be easily
controlled by changing the electrodeposition process condi-
tions, namely the electrolytic bath composition.
Acknowledgments
The authors would like to thank Fundaça~ o para a Cie
^ ncia e a
Tecnologia (FCT, Portugal) for contract no. IF/01084/2014/
CP1214/CT0003 under IF2014 Programme (D.M.F. Santos),
grant SFRH/BD/123963/2016 and for the financial support
under projects PEst-OE/QUI/UI0100/2013 and M-ERA-NET/
0004/2014 “Fabrication and functionalisation of nano-
structured metallic foams for energy storage applications”.
1708 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 ) 1 7 0 1 e1 7 0 9
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2018.11.070.
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