MnO2-coated Ni nanorods: Enhanced high rate behavior in pseudo-capacitive supercapacitor

Article abstract of DOI:10.1016/j.electacta.2010.03.012

Ni nanorods prepared by electrochemical growth through an anodized aluminium oxide membrane were used as substrate for the electrodeposition of MnO₂ either in potentiostatic mode or by a pulsed method. Electrochemical deposition parameters were chosen for an homogeneous deposit onto Ni nanorods. Resulting Ni supported MnO₂ electrodes were tested for electrochemical performances as nanostructured negative electrodes for supercapacitors. They exhibited initial capacitances up to 190 F/g and remarkable performances at high charge/discharge rates.

Full text of DOI:10.1016/j.electacta.2010.03.012

Electrochimica Acta 55 (2010) 7454–7459
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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
MnO2-coated Ni nanorods: Enhanced high rate behavior in pseudo-capacitive
supercapacitor
Y. Leia, B. Daffosb, P.L. Tabernab, P. Simonb,1, F. Faviera,∗,1
a Institut Charles Gerhardt Montpellier – AIME, UMR 5253, Université Montpellier 2, Place Eugène Bataillon, 34095 Montpellier Cedex 5, France
b CIRIMAT UMR CNRS 5085, Université Paul Sabatier Toulouse 3, 31062 Toulouse Cedex 4, France
a r t i c l e i n f o
a b s t r a c t
Article history:
Ni nanorods prepared by electrochemical growth through an anodized aluminium oxide membrane were
used as substrate for the electrodeposition of MnO2 either in potentiostatic mode or by a pulsed method.
Electrochemical deposition parameters were chosen for an homogeneous deposit onto Ni nanorods.
Resulting Ni supported MnO2 electrodes were tested for electrochemical performances as nanostructured
negative electrodes for supercapacitors. They exhibited initial capacitances up to 190 F/g and remarkable
performances at high charge/discharge rates.
Received 22 September 2009
Received in revised form 3 March 2010
Accepted 5 March 2010
Available online 16 March 2010
Keywords:
© 2010 Elsevier Ltd. All rights reserved.
Supercapacitor
Manganese dioxide
Coating
Nanorods
High rate capacitance
1. Introduction
has been previously developed and electrochemical performances
of MnO2-coated carbon with small mesopores [7] or carbon nan-
MnO2 was first proven as performing electrode material for
supercapacitors by Goodenough and co-workers [1,2]. The eluci-
dation of the charge storage mechanism involving the Mn4+/Mn3+
redox couple led to the calculation of a maximum theoretical capac-
itance of 1100 F/g for a 1 V electroactive potential range [3,4].
However, highest reported capacitances for bulk electrodes have
never reached such a high value, but merely 300 F/g [5,6]. Among
the main causes pointed out for these limited performances, the
limited charge percolation behavior through the material thanks
to the poor electrical conductivity of MnO2. Therefore, the use
of MnO2 thin films appears an attractive potential route to over-
come this limit: electrochemical reactions at the electrolyte and
active material interface take place only few nanometers apart from
the current collector (CC) where generated charges are collected.
Performances are improved in terms of gravimetric capacitance rel-
ative to MnO2 content but the total energy stored by the device is
however limited by the small quantity of deposited active material
at the planar CC surface. The use of nanostructured CC develop-
ing larger surface areas makes then obvious sense. This strategy
otubes [8] composite electrodes have been reported to capacitances
at 220 F/g and 141 F/g respectively. The limited accessibility of liq-
uid electrolyte to the whole mesoporous volume as well as the
limited charge percolation have been pointed out to explain these
somehow disappointing performances. Depositing very thin MnO2
films on flat Ni current collectors has led to impressive capacitance
values up to 400 F/g [4]. On the other hand, 200 F/g capacitances
have been obtained from MnO2 deposited onto Ni substrates nanos-
tructured by etching [9].
We have recently reported the preparation of mesoporous
carbon/MnO2 composite electrode material and showed that the
capacitance extracted from MnO2 deposited at the surface of large
mesopores (up to 150 nm in diameter) could reach high value up to
900 F/g (relative to MnO2 weight content), close to the maximum
theoretical one [10]. However, the capacitance of the compos-
ite electrode itself did not exceed 180 F/g because of the low
MnO2 content (9 wt% for the most performing electrode) and the
corresponding dead-weight from the mesoporous carbon current
collector. It is also anticipated that electrochemical performances
could be improved by a more homogeneous dispersion of the active
material into the porous volume. In that matter, anodic deposition
is an easy and efficient method to perform on monolithic sub-
strates as suggested by recent works from Chang et al. [4]. They
prepared a nanostructured Ni electrode after a selective electro-
chemical stripping of Cu contained in their pristine Cu–Ni alloy
co-deposited on an indium-doped tin oxide substrate (ITO). Their
∗
Corresponding author at: Institut Charles Gerhardt Montpellier – AIME, UMR
5253, Université Montpellier 2, Place Eugène Bataillon, cc 1502, 34095 Montpellier
Cedex 5, France. Tel.: +33 4 67 14 33 32; fax: +33 4 67 14 33 04.
E-mail address: fredf@univ-montp2.fr (F. Favier).
1
ISE member.
0013-4686/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2010.03.012

Y. Lei et al. / Electrochimica Acta 55 (2010) 7454–7459
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prepared MnO2/Ni composite electrode exhibited attractive val-
ues of capacitance relative to MnO2 content up to 500 F/g. On the
other hand, as CC supporting Li-ion battery anode materials, such
nanorod architectures have shown they can remarkably accom-
modate high charge/discharge rates up to a complete charge or
discharge in few minutes using Fe3O4 [11], SnO2 [12] or other active
materials [13,14]. As a critical step for electrochemical performance
in supercapacitors, the charge/discharge behavior of MnO2 sup-
ported on ordered Ni nanorods remains unexplored.
In this paper, we are presenting an original electrochemical
route forthecontrolleddepositionofanMnO2 coating at the surface
of well defined Ni nanorods as well as an exploration of the elec-
trochemical behavior of the prepared nanostructured electrodes
especially towards charge/discharge rate.
was determined by integration of the total coulombic charges used
for deposition over electrolysis durations. Weights were evaluated
at mMnO = 0.254 mg and 0.339 mg for the two-step depositions
onto Ni2nanorods at 0.85 V for 3600 s and 7200 s respectively.
0.250 mg of MnO2 was deposited by two-step electrolysis at 0.85 V
for 3600 s onto the flat Ni foil. The total charge Q was calcu-
lated by integration of the measured current with respect to the
time of deposition. This led to the weight of deposited material
mMnO = Q × MMnO2 /2F, with F the Faraday constant. This weight
2
is however over-estimated since at working potentials of 0.85 or
1.0 V/Ag–AgCl, a part of the charge is used for water oxidation and
oxygen evolution.
2.3. Characterizations
The resulting electrodes were analyzed by Scanning Electron
Microscopy (SEM, JEOL JSM6300F), Cyclic Voltammetry (CV) and
Electrochemical Impedance Spectrosocopy (EIS).
2. Experimental
2.1. Ni nanorods
The electrochemical cell was a conventional three electrode
cell composed of an Ag–AgCl as reference electrode, a Pt foil
as counter-electrode and the composite electrode as working
electrode. Electrochemical characterizations were performed in a
K2SO4 0.5 M electrolytic solution at room temperature using a Bio-
logic VMP3 potentiostat running under EC-Lab software.
Ni nanorods supported onto Ni foil (250-␮m thick, 10 mm diam-
eter, 99% Ni, Goodfellow) were prepared following a procedure as
described in a previous work [11]. A two-electrode electrochem-
ical cell was used. It included a polished Ni surface as cathode
and a Ni anode separated by a Whatman paper and an AAO mem-
brane. Whatman paper was used as separator and AAO membrane
(Whatman, Anodisc 47, reference #6809 5022) as template for the
electrochemical growth of Ni. The plating solution was composed
of NiSO4·6H2O (240 g/L), NiCl2·6H2O (20 g/L) and H3BO3 (20 g/L)
(Acros Chemicals). Using an Arbin BT2000 potentiostat, a two-step
cathodic current pulse method was used for the preparation: (a)
−15 mA/cm2 for 50 ms (germination step) then (b) −1 mA/cm2 for
250 ms (growth step).
3. Results
3.1. Raw Ni nanorods
The SEM picture showed in Fig. 1a depicts a quite perfect and
dense array of Ni nanorods after dissolution of the AAO mem-
brane. They are about 200 nm in diameter and 5 ␮m long. As
electrochemically grown onto the Ni electrode, they are strongly
mechanically and electrically bonded to the metal substrate build-
ing a self-supported nanostructured electrode suitable for further
active material electrodepositions and tests. As shown in Fig. 2a
from a CV in K2SO4 0.5 M at s = 10 mV/s, this electrode made
of raw Ni nanorods exhibits a very limited capacitive behavior
(3.5 mF/cm2 relative to the footprint area of the Ni substrate) in
a narrow electrochemical window (from −0.3 to 0.3 V/Ag–AgCl).
Fig. 2b shows a CV of the same electrode in the same potential
window as usually used for the electrochemical investigations on
MnO2-based electrode material (from −0.05 V to 0.85 V/Ag–AgCl).
Actually, it mostly shows the oxygen evolution reaction occur-
ring at Ni surface at potentials higher than 0.6 V/Ag–AgCl. MnO2
deposition potential was extracted from CVs performed in MnSO4
2 mM and K2SO4 25 mM plating solution (Fig. 3). An oxidation
peak (EOx) corresponding to the oxidation on Mn2+ to Mn4+ and
MnO2 surface deposition was observed at about 1.0 V. A poten-
tial window from 0.85 V to 1.0 V was found as suitable for MnO2
deposition.
2.2. MnO2 coating
Prior to the anodic deposition of MnO2, AAO membrane was dis-
solved in NaOH 1 M (VWR International) etching solution at 80 ◦C
for 3 min. MnO2 plating solution was composed of MnSO4 2 mM
and K2SO4 25 mM (99%, Aldrich) [15]. Ni nanorods were soaked
with this solution by a vacuum-assisted impregnation method.
MnO2 coating was first performed by a single-step potentiostatic
method, at Ework potentials at 0.85 V and 1.0 V versus Ag-AgCl for
900 s, 1800 s and 3600 s. For comparison purpose, the same electro-
chemical parameters were used for the single-step potentiostatic
deposition of a layer of MnO2 onto a flat Ni foil (Goodfellow). Ni foil
was degreased using acetone before use. Alternatively a two-step
potentiostatic pulse method was also used: first step at 0.85 V for
10 s then second step at open circuit voltage (OCV) for 2 s. In that
case, the deposition duration corresponded to the time at 0.85 V.
For example, the two-step method was repeated 360 times in order
to achieve a deposition of 3600 s. The weight of deposited MnO2
Fig. 1. SEM micrograph of raw Ni nanorods (a) used as substrate for the electrodeposition of MnO2 and MnO2 electrodeposited at 1.0 V/Ag–AgCl for 3600 s (b) and at
0.85 V/Ag–AgCl for 1800 s (c) on Ni nanorods.

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Y. Lei et al. / Electrochimica Acta 55 (2010) 7454–7459
Fig. 2. CV measured of raw Ni nanorods in K2SO4 0.5 M to evaluate its capacitance (a) and its stability in a larger potential range (b).
material growth. This rest step aims to limit the Mn2+ ions deple-
tion close to the Ni surface, avoiding thus a diffusion-controlled
deposition reaction. MnO2 depositions were carried out for 3600 s
(360 cycles of the two-step method) and 7200 s (720 cycles). SEM
pictures in Fig. 5 show the electrode surface after 3600 s (a) and
7200 s (b) deposition times. Micrographs show that the voids in
between the nanorods are filled more homogeneously using these
electrodeposition experimental parameters. The whole surface of
the nanorods, top and sides, is covered by an MnO2 layer whose
thickness obviously depends on the electrolysis duration or num-
ber of electrolysis cycles. However, some voids are still present
between the rods to allow electrolyte impregnation. The layered
nanostructure is clearly evidenced by electronic contrast showing
the bright Ni core of the nanorods and the gray MnO2 deposit.
The capacitance of the 3600 s-electrode was evaluated by CV
ran at various scan rates. The evolution depicted in Fig. 6a shows
that capacitances are hardly affected by the scan rates even at high
scan rates while remaining close to 100 F/g. The electrochemical
capacitance of the 7200 s-electrode was measured at C1 = 190 F/g
for the first cycle. This quite high value progressively fade down
upon cycling and, after 500 cycles, a 20% loss was observed with
C500 = 150 F/g.
3.2. MnO2 coating, single-step potentiostatic method
Ni nanorods were first used for MnO2 electrodeposition at con-
stant potentials, respectively 1 V and 0.85 V/Ag-AgCl. SEM picture
in Fig. 1b shows that, at 1.0 V/Ag-AgCl potential, most of MnO2 was
deposited at the top of the nanorods. The same deposit morphol-
ogy was obtained whatever the electrolysis duration. In contrast,
at Ework sets to 0.85 V/Ag-AgCl, Ni nanoplot surface could be more
homogeneously coated by MnO2 (Fig. 1c) for both 1800 s and 3600 s
electrolysis durations. At both working potentials, MnO2 deposits
are composed of dense layers or aggregates of highly disordered
nanosheets. The evaluation of electrochemical performances by
CV measurements (Fig. 4) exhibits capacitances about C1 = 130 F/g
at first charge/discharge cycle. This initial capacitance value from
MnO2 deposit obtained at 0.85 V/Ag-AgCl strongly decreases during
the first 100 cycles before to stabilize at 80 F/g after 500 cycles. In
contrast, the low capacitance value at 80 F/g obtained at first cycles
for MnO2 deposit prepared at 1.0 V/Ag-AgCl, slowly increases upon
cycling up to 100 F/g after 500 cycles (Fig. 4b).
3.3. MnO2 coating, two-step potentiostatic method
To improve the deposit morphology onto the nanorods, an alter-
native two-step potentiostatic method has been used. It included
a rest period at open circuit after a short potentiostatic pulse for
3.4. Electrochemical impedance spectroscopy (EIS)
EIS analyses were performed at open circuit voltage (OCV) in
K2SO4, 0.5 M after 1–5–10–50–100–500 cycles of charge/discharge
at 10 mV/s scan rate. The MnO2/Ni nanorods composite electrodes
were stabilized at OCV for 1 hour prior to the experiments per-
formed with U = 10 mV around OCV in the 10−2 to 50.103 Hz
frequency range. The corresponding Nyquist plots depicted in Fig. 7
were fitted by the Zfit routine from EC-Lab software, used to mon-
itor the experiments.
For the electrode prepared by the single pulse method, EIS
analyses did not show any loop at high frequencies characteristic
to parallel RC circuit for composite highly porous electrode. Nei-
ther could be observed any Warburg-like element, characteristic
to semi-infinite diffusion or migration in the porous structure of
the electrode [16]. Nyquist plots are characteristic of the non-ideal
capacitance behavior of the thick MnO2 layer deposited onto Ni
nanorods since the increase of the imaginary part of the impedance
at low frequency deviated from the theoretical vertical line. This
non-ideality may originate from slow MnO2 dissolution as sol-
vated Mn3+ or redox leaking currents from impurities present in the
electrolyte like dissolved oxygen. For the electrodes prepared by
Fig. 3. CVs performed in the platting solution using a Ni nanorods substrate.

Y. Lei et al. / Electrochimica Acta 55 (2010) 7454–7459
7457
Fig. 4. CV of MnO2-coated Ni nanorods (single-step method, 1 V for 900 s) in K2SO4 0.1 M (a). Evolution of capacitance upon cycling of an MnO2-coated Ni nanorods electrode
(b). Deposition performed by single-step potentiostatic method at 1.0 V for 900 s (triangles, mMnO = 0.0177 mg) and at 0.85 V for 1800 s (squares, mMnO = 0.0545 mg).
2
2
Fig. 5. MnO2 deposited by two-step potentiostatic pulse method at 0.85 V for 3600 s (a) and 7200 s (b) on Ni nanorods.
the two-step pulsed method, Nyquist plots exhibit a semi-infinite
4. Discussion
diffusion (Warburg element) as well as a non-ideal capacitance
behavior. A small loop might also be observed at high frequencies.
Above 50 cycles, the general shape of the plots changes and the
low frequency capacitive behavior shifts along the X-axis to higher
resistance.
4.1. Single-step potentiostatic method
Use of a high anodic working potential (anodic over-potential)
leads to an uncontrolled growth of MnO2 onto Ni nanorods. At 1.0 V,
Fig. 6. Evolution of capacitance versus scan rates (a) for MnO2-coated Ni nanorods (squares, two-step potentiostatic pulse method, 0.85 V for 3600 s) and MnO2-coated Ni
flat substrate (ꢀ, two-step potentiostatic pulse method, 0.85 V for 3600 s). Capacitances are relative to the weight of deposited MnO2 and geometric surface of the electrode.
Evolution of capacitance upon cycling (b) of an MnO2-coated Ni nanorods electrode (two-step potentiostatic pulse method, 0.85 V for 7200 s).

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Y. Lei et al. / Electrochimica Acta 55 (2010) 7454–7459
Fig. 7. EIS analyses upon cycling were performed on Ni nanorods coated by MnO2 by single-step method (at 0.85 V for 900 s (a) and by two-step potentiostatic pulse method
for 7200 s (b)).
the growth kinetics are so high as compared to the diffusion of
Mn2+ through the nanoplot network that quickly, species suitable
for oxidation are made available only at the top surface of the elec-
trode, which is easily accessible for mass transfer. At such a high
potential, the growth mechanism is similar to that on a flat elec-
trode: deposit is quite thick and covers only the top of the nanorods
(Fig. 1b). Another effect can account for this behavior since the high
current density induced by tip effect favors MnO2 deposition pref-
erentially on the nanoplot tops. Decreasing the potential applied to
0.85 V obviously allows a better control for a more uniform growth
of MnO2 in between the nanorods as well as on their tops (Fig. 1c).
The decrease of the anodic over-potential allows a more kinetically
controlled oxidation process more compatible with the diffusion of
Mn2+ species to the electrolyte/electrode interface. At such a poten-
tial, the corresponding current density is however rather limited as
is the quantity of deposited MnO2.
A comparison of the capacitances measured from the CVs for
raw nickel nanorods (Fig. 2b) and those for the same nanostruc-
tured substrate covered with a MnO2 layer (Fig. 4a) demonstrates
that, the electrochemical contribution of Ni substrate to the overall
electrode capacitance is fairly limited (less than 5%) whatever the
electrolysis parameters selected for the deposition of MnO2. This
limited contribution originates from the oxidation of Ni metal to
form an Ni(OH)2 protective passivation layer [18]. It also depends
on the coverage of the nickel substrate by MnO2 layer. As shown in
Fig. 2b, Ni passivation occurs mild pH range at potential greater
than 0.3 V/Ag/AgCl. The electrode prepared by MnO2 deposition
at 1.0 V shows a behavior close to what is usually observed for
a MnO2-based bulk electrode, i.e. capacitance increases during
the first tens of cycles before to stabilize to a threshold value
(Fig. 4b) [19]. This behavior points out that MnO2 layer is, in this
case, quite thick. The same behavior has already been observed
for thick MnO2 films precipitated at the surface of porous carbons
[10].
the nanostructure towards the nanoplot surface where the oxida-
tion to Mn4+ and subsequent MnO2 deposition proceed. A pulse
method has been developed to allow an optimal supplying of Mn2+
species in the constrained volume built by the nanoplot network,
making them available for oxidation at the platting solution/nickel
nanoplot interface.
4.2. Two-step potentiostatic method
The working potential at 0.85 V was applied for 10 s and fol-
lowed by a resting step at open circuit voltage (OCV) for 2 s. This
scheme has been repeated over 360 and 720 cycles. By using this
method, Ni nanorods appeared as coated individually by MnO2
(Fig. 5). To evaluate the weight of deposited MnO2 (mMnO2 ), the
total charge has been calculated by integration of the current of
each 0.85 V step through 10 s electrolysis duration. From this more
homogeneous MnO2 layer, higher performances were expected and
hence initial capacitance was measured at C1 = 190 F/g. The capac-
ity retention, far from perfect, was improved too since the capacity
loss was limited to 20% after 500 cycles (Fig. 6b).
For electrodes prepared by both deposition approaches capacity
fadings are characteristic of a progressive dissolution of the elec-
troactive material thanks to obviously too high upper potential
limit used for these long term cycling tests. The potential win-
dow used was first adjusted to extract the highest initial capacity
and has obviously not been optimised for long term cycling. It also
corresponds to the potential window used in previous studies on
capacitive behavior of MnO2 electrodeposited on stainless-steel
substrates [15].
As demonstrated in Fig. 6a, the most remarkable result lies in the
maintain of high capacitance values of the 3600 s-electrode under
high charge/discharge rate. For comparison purpose, MnO2 was
electrodeposited on a flat Ni substrate using the same electrolysis
parameters as previously described for the 3600 s-electrode. Elec-
trode surface composed of disordered MnO2 nanosheets is close
to what has been observed for MnO2 deposits onto flat stainless-
steel surfaces [15]. Fig. 6a depicts the capacitance of such a deposit
as a function of the applied scan rate: the higher the scan rate,
the lower the capacitance. The same behavior has been observed
using thin films deposited onto flat Ni current collectors. It is
characteristic of MnO2 bulk electrode for which capacitances are
fading for higher scan rate because of the diffusion limitation
of electrolytic species in the material structure [21]. In contrast,
the maintain of the capacitance in the whole scan rate range
explored in this study, can be explained by the facile diffusion
of electrolyte ions through the open structure provided by Ni
nanorods.
In contrast, the capacitance of Ni nanoplot supported MnO2 pre-
pared at 0.85 V quickly fades down upon cycling as demonstrated
by the 30% loss of the initial capacitance after 500 cycles (Fig. 4b).
This trend is characteristic of a thin layer of active material. This
later point is also supported by the initial capacitance at 135 F/g,
higher than the initial capacitance measured for the electrode pre-
pared by deposition at 1.0 V. Noteworthy is the relatively low value
for this initial capacitance while MnO2 thin films have shown
capacitances up to 900 F/g [20]. Obviously, decreasing the work-
ing potential from 1.0 V to 0.85 V has enhanced the homogeneity
of the deposit and improved the electrochemical performances of
the MnO2/Ni nanorods electrode. However in both cases, the depo-
sition remains controlled by diffusion of the Mn2+ species through

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4.3. Electrochemical impedance spectroscopy (EIS)
and pulse potentiostatic methods have been used resulting in the
deposition of MnO2 of distinct morphologies. The latter method
led to more homogeneous deposits at the nanoplot surfaces for a
maintain of the original open structure. The best electrochemical
performances exhibited capacitances up to 190 F/g with a loss of
about 20% after 500 cycles. The evaluation of the scan rate impact on
capacitance pointed out an outstanding behavior: in contrast with
what is usually observed for bulk MnO2-based electrodes, in the
present cases, capacitances remain high at high charge/discharge
rates. This behavior was confirmed by EIS analyzes showing that
MnO2-coatings seem thin enough and uniformly distributed to give
the prepared MnO2/Ni electrode a porous structure facilitating the
diffusion of electrolytic species through the whole electrode vol-
ume. Such remarkable behavior highlights potential applications
for these prepared MnO2/Ni nanorods electrodes in high-power
micro-devices.
EIS analyses confirm the idea of a diffusion of electrolyte through
the MnO2-coated Ni nanorods facilitated by the electrode open
structure and leading to high capacitances at high scan rates. The EIS
plot in Fig. 7a is typically the one observed for a compact MnO2 film
since there is no diffusion limitation. However, the absence of any
diffusion like behavior at 45◦ generally observed for highly porous
electrodes [16,17] and usually described using a Transmission Line
Model of a combination of series—parallel RC circuits [16] evidences
the absence of porosity inside the MnO2 film structure. The change
in the plot slope above 50 cycles in the low frequency region where
the capacitive behavior can be seen indicates an increase of the
charge transfer resistance during cycling that can be assigned to
the slow dissolution of MnO2.
The main differences with the plot presented in Fig. 7b is the
presence of a Warburg-like sloppy behavior in the middle fre-
quency range [16]. This stands for the ion migration inside the
porosity of the electrode: the lower the frequency, the deeper the
penetration of ions from the electrolyte into the depth of the elec-
trode [17]. The MnO2 coating obtained under pulsed galvanostatic
conditions was found to be thin and conformal onto the Ni rods,
leading to an open porous structure for the whole film as compared
to what was obtained in Fig. 7a. The EIS plots confirm this difference.
Another difference between the two films is that the low frequency
range of the Nyquist plot in Fig. 7b is not so affected by the cycle
number as compared to Fig. 7a. The MnO2 dissolution, responsible
for the change observed in Fig. 7a for potentiostatic deposited films,
is slowing down for MnO2 films with an open porous structure
thanks to the Ni nanorods. In Fig. 7b, an increase in the impedance
at high frequency is measured after 500 cycles. Since it is the dom-
inant effect in this frequency range, it is usually associated to an
increase in the electrolyte resistance upon cycling. This is usually
true, as long as electrode remain unchanged, both chemically or
geometrically. In the present case, it certainly comes from a resis-
tance increase upon cycling because of the progressive passivation
of the electrode at the solid–liquid interface. The generation of a
complex nickel/manganese oxide such as NiMnO2 at the interface
could originate for the observed impedance increase.
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5. Conclusions
Ni nanorods prepared by electrochemical growth through a
porous AAO membrane have been successfully used as substrate
for the controlled electrochemical deposition of MnO2. Continuous