Materials Letters 70 (2012) 11–15

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Comparison of open porous copper structures obtained by the different current

regimes of electrolysis
Nebojša D. Nikolić a,⁎, Goran Branković b
a
ICTM-Institute of Electrochemistry, University of Belgrade, Njegoševa 12, Belgrade, Serbia
b
Institute for Multidisciplinary Research, Kneza Višeslava 1a, Belgrade, Serbia

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

Article history: Formation of open porous copper structures by the electrodeposition processes in the hydrogen co-
Received 17 August 2011 deposition range was considered. Morphologies of copper deposits obtained by the reversing current (RC) re-
Accepted 4 November 2011 gimes at the same average current density but with the different the anodic current density/anodic pulse ra-
Available online 29 November 2011
tios were compared with those obtained by the pulsating current (PC) regime at the same average current
density and in the constant galvanostatic mode at the current density which was equal to this average cur-
Keywords:
Electrodeposition
rent density. The considerable increase of the specific surface area of the honeycomb-like structures, deter-
Copper mined by the increase of number of holes, as well as by the decrease of both holes size and wall width
Hydrogen among them, can be attained if the appropriate parameters of the RC regimes are applied. In this way, it is
Morphology shown that the regime of reversing current (RC) is superior in the production of open porous structures suit-
Microstructure able to be used as electrodes in many electrochemical devices in relation to other current regimes of electrol-
Electron microscopy ysis, such as the PC and the galvanostatic regimes.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction effort is moved to the formation of these electrodes by periodically

changing regimes of electrolysis, such as pulsating overpotential
Electrodeposition is a very suitable way to get open porous struc- (PO) [4,5], pulsating current (PC) [6,7] and reversing current (RC)
tures with the extremely high surface areas, which are ideally suited [8] ones. Effects of the application of these regimes of electrolysis on
for electrodes in many electrochemical devices, such as fuel cells, batte- the formation of the honeycomb-like electrodes were equivalent to
ries and chemical sensors [1]. The procedure of formation of these elec- those attained by the addition of additives to the electroplating
trodes by electrodeposition techniques is known as gas bubble dynamic baths [3,9]. In this paper, using well known fact that electrodeposition
template method where hydrogen bubbles generated by electrodeposi- processes at periodically changing rate in the millisecond range occur
tion at high overpotentials or current densities act as dynamic template at the average current density [10,11], comparison between copper
around which metal electrodeposition occurs. The main characteristics structures obtained by electrodeposition in the hydrogen co-
of electrochemically formed open porous electrodes, known as the 3D deposition range by the different PC and RC regimes at the same av-
foam or the honeycomb-like ones, are holes formed of detached hydro- erage current density was made. The obtained copper structures
gen bubbles and cauliflower-like agglomerates of metal grains or den- were also compared with the one obtained at the constant current
drites formed around them [1,2]. The specific surface area of these density which was equal to this average current density.
structures is determined by the number and size of holes, as well as
by wall width among them [3]. One of the main challenges in the devel- 2. Experimental
opment of these technologically important electrodes is the increase of
their specific surface area, i.e. formation of the honeycomb-like elec- Copper electrodeposition was performed from 0.15 M CuSO4 in
trodes with the maximal number of holes and the minimal size of 0.50 M H2SO4, at the room temperature using cylindrical copper
holes and the wall width among them. The easiest way to reach it is wires as working electrodes. The counter electrode was of pure cop-
the choice of regimes of electrolysis and electrodeposition conditions. per. Copper was electrodeposited in the galvanostatic regime and by
The conditions of the formation of open porous electrodes by the the regimes of pulsating (PC) and reversing (RC) current.
constant regimes of electrolysis (the potentiostatic and galvanostatic Copper was electrodeposited galvanostatically at a current density of
ones) are well examined and systematized [1,2]. In the last time, the 120 mA/cm2 (this type of electrolysis is further denoted as DC regime).
In the PC regime, the current density amplitude of 440 mA/cm 2,
deposition pulse of 10 ms and pause duration of 26.6 ms were select-
⁎ Corresponding author. Tel./fax: + 381 113370389. ed. For these parameters PC regime, the average current density was
E-mail address: [email protected] (N.D. Nikolić). 120 mA/cm 2 (this type is further denoted as PC).

0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.11.081
12 N.D. Nikolić, G. Branković / Materials Letters 70 (2012) 11–15

For the regime of the reversing current (RC), the average current a 0,5 40
density, iav is given by Eq. (1) [11]: and RC40; η I,av(H2) = 22.1%
and RC200; η I,av(H2) = 21.2% 35
RC520; η I,av(H2) = 22.8%
iav ¼ ðic t c –ia t a Þ=ðt c þ t a Þ ð1Þ 0,4 and
30
where: ic — the cathodic current density, ia — the anodic current density,

η I,av(H2)/ %
0,3 25
tc — the cathodic pulse duration and ta — the anodic pulse duration.

V/ cm3
In all RC experiments, ic of 440 mA/cm2 and tc of 10 ms were ap- 20
plied. The average current density of 120 mA/cm2 was selected, what 0,2
15
is attained by the regulation of ratios between the anodic current den-
sity, ia and the anodic pulse duration, ta. Then, the following parameters 10
0,1
of RC regimes were analyzed:
5
a) ia = 40 mA/cm 2; ta = 20 ms (denoted as RC40)
0,0
b) ia = 200 mA/cm 2; ta = 10 ms (denoted as RC200) 0
0 50 100 150 200 250 300
c) ia = 520 mA/cm 2; ta = 5 ms (denoted RC520).
t/ s
Copper was electrodeposited with quantities of electricity of
10 mAh/cm 2. b 0,5 40
The obtained copper deposits were examined using scanning elec- and DC mode; η I,av(H2) = 22.7%
and PC; η I,av(H2) = 21.2% 35
tron microscope — TESCAN Digital Microscopy.
The average current efficiency of hydrogen evolution, ηI,av(H2), 0,4
30
was determined using the experimental procedure described in

η I,av(H2)/ %
Refs. [6–8]. 0,3 25

V/ cm3
20
3. Results and discussion
0,2
15
The dependences of the volumes of evolved hydrogen and the aver-
age current efficiencies of hydrogen evolution on electrolysis time 10
0,1
obtained for the different RC, the PC and the DC regimes are shown in
5
Fig. 1a and b, respectively. There was no any gas evolution during anod-
ic pulses in the RC regimes indicating that the overall gas evolution cor- 0,0 0
responds to hydrogen evolution [8]. From Fig. 1, it can be seen that both 0 50 100 150 200 250 300
the quantities of evolved hydrogen and the average current efficiencies t/ s
of hydrogen evolution did not depend on the applied current regimes of
Fig. 1. The dependences of the volume of evolved hydrogen and the average current effi-
electrolysis (ηI,av(H2) = 22.0 ± 0.8%). It is understandable due to the fact
ciency of hydrogen evolution on electrolysis time for copper electrodeposition by:
that electrodeposition processes in the millisecond range at periodically a) RC40, RC200 and RC520 regimes; and b) PC and DC regimes.
changing rate occur at the average current density [11].
Fig. 2 shows morphologies of electrodeposited copper obtained by
the different RC regimes (RC40 — Fig. 2a; RC200 — Fig. 2b and
RC520 — Fig. 2c), by the PC regime (PC — Fig. 2d) and in the constant about 50 μm, while holes obtained in the DC mode were about
galvanostatic mode (DC — Fig. 2e). As already mentioned, the average 100 μm. The average wall widths in the honeycomb-like structures
current density was the same in all analyzed PC and RC regimes obtained by the RC40 and RC200 regimes were 24 and 28 μm, respec-
(iav = 120 mA/cm 2), while the applied current density in the DC tively, and they were considerably smaller than the average wall
mode corresponded to this average current density. From Fig. 2, it width in the honeycomb-like structure obtained in the DC mode
can be seen that the obtained surface morphologies can be classified (70 μm). The part of morphologies of deposits among holes (or the
in the two groups. In the first group are the honeycomb-like struc- part of the wall width) obtained by the RC40 regime and the DC mode
tures obtained by the RC40 (Fig. 2a), RC200 (Fig. 2b) and DC regimes are shown in Fig. 3c and d, respectively. The cauliflower-like agglomer-
(Fig. 2e). The characteristic of the second group of the obtained cop- ates of grains with small dendrites on them were formed by the RC40
per deposits is the dominant presence of dish-like holes and indepen- (Fig. 3c) and RC200 regimes. The nucleation exclusion zones can be
dently formed cauliflower-like agglomerates of copper grains. These clearly observed around these cauliflower-like agglomerates of copper
morphological forms were obtained by the RC520 (Fig. 2c) and PC grains. On the other hand, the relatively large cauliflower-like copper
(Fig. 2d) regimes. grains agglomerates surrounded by deep irregular channels which the
From Fig. 2a, b and e, a clear difference can be seen in the size and origin is of evolved hydrogen were formed in the DC mode (Fig. 3d).
number of holes, as well as in the wall width among them in the Anyway, it is clear that application of the appropriate RC regime led to
honeycomb-like structures obtained by the RC40 and RC200 regimes redistribution of evolved hydrogen decreasing the contribution of gen-
and those obtained at the constant current density. The number of erated hydrogen to the creating of channel structure through the interi-
holes, the size of holes and the wall width among them were estimated or of the deposit and increasing the compactness of the formed
by the quantitative analysis of the SEM micrographs shown in Fig. 2, as structures (the current density distribution effect).
well as those recorded at the higher magnifications. The number of Dish-like holes were the dominant type of holes obtained by the
holes formed by the RC40 and RC200 regimes (350 and 280 holes per PC and RC520 regimes. The typical dish-like hole obtained by the PC
mm2 copper electrode, respectively) was considerably larger than the regime is given in Fig. 3e. The average diameter of this type of holes
number of holes formed in the DC regime (115 holes per mm 2 copper was about 100 μm. The cauliflower-like agglomerates of grains, as
electrode). The typical holes obtained by the RC40 and the DC mode well as the mixture of cauliflower-like grains agglomerates and den-
are shown in Fig. 3a and b, respectively. The holes obtained by the drites were formed by the PC and RC520 regimes, respectively. The
RC40 and RC200 regimes were about twice smaller than those obtained typical independently formed cauliflower-like agglomerate of copper
at the constant current density. The average size of these holes was grains obtained by the PC regime is presented in Fig. 3f.
 N.D. Nikolić, G. Branković / Materials Letters 70 (2012) 11–15 13

Fig. 2. Copper deposits obtained by: a) RC40; b) RC200; c) RC520; d) PC and e) DC regimes.

Hydrogen evolution responsible for the formation of the that the diffusion layer of the macroelectrode was not disturbed during
honeycomb-like electrodes was vigorous enough to cause such stirring the formation of these morphological forms.
of the copper solution which leads to the decrease of the cathode diffu- From technological point of view, the first group of copper de-
sion layer thickness and to the increase of the limiting diffusion current posits (the honeycomb-like structures) is especially important for
density and hence to the change of the hydrodynamic conditions in the the application as electrodes in electrochemical devices [1]. It is
near-electrode layer [2]. The concept of the “effective overpotential” shown that the size of holes and the wall width among holes were de-
was proposed to explain the formation of this structure type. On the creased, while the number of holes was increased when the appropri-
other hand, the appearance of dish-like holes, independently formed ate RC parameters were applied (RC40 and RC200). Hence, comparing
cauliflower-like grains agglomerates and dendrites clearly indicated the number of the formed holes, their size and the wall width among
14 N.D. Nikolić, G. Branković / Materials Letters 70 (2012) 11–15

Fig. 3. The typical holes obtained by: a) RC40; b) DC; and e) PC regimes, and morphological forms obtained among holes by: c) RC40; d) DC; and f) PC regimes.

them, it can be concluded that the specific surface area of the application of square-waves RC, what can be explained by the as-
honeycomb-like electrodes was increased by the application of the sumption that during anodic pulses the adatoms in nonstable posi-
appropriate RC regime making this regime superior in relation to tions dissolve faster than atoms in stable position in lattice [11].
other current regimes of electrolysis, such as the PC and DC regimes.
The increase of the specific surface area of this electrode type through 4. Conclusions
the increase of number of holes and the decrease of both hole size and
the wall width among them were also observed by the addition of the The effect of the regime of reversing current (RC) on the formation
corresponding additives to the electrodeposition solutions [3,9]. The of open porous structures of copper was examined by the technique
compactness of the honeycomb-like structure was increased by the of scanning electron microscopy. Copper structures obtained by
 N.D. Nikolić, G. Branković / Materials Letters 70 (2012) 11–15 15

different square-waves RC were compared with those obtained by the References

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Acknowledgement York: Kluwer Academic/Plenum Publishers; 2002.

The work was supported by Ministry of Education and Science of

Republic of Serbia (No. 172046).