Electrochemistry Communications 48 (2014) 164168

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Short communication

QCM-D studies of polypyrrole inuence on structure stabilization of

phase of Ni(OH)2 nanoparticles during electrochemical cycling
Fernando H.C. Miguel, Tnia M. Benedetti , Roberto M. Torresi, Susana I. Crdoba de Torresi
Instituto de Qumica, Universidade de So Paulo, CP 26077, 05513-970 So Paulo, Brazil

a r t i c l e

i n f o

Article history:
Received 5 August 2014
Received in revised form 8 September 2014
Accepted 12 September 2014
Available online 19 September 2014
Keywords:
Nickel hydroxide
Polypyrrole
Quartz crystal microbalance with dissipation

a b s t r a c t
Pure badly crystallized, bc-Ni(OH)2, and hybrid bc-Ni(OH)2/polypyrrole nanoparticles (NPs) were synthesized and immobilized by electrophoretic deposition. The inuence of polypyrrole (Ppy) on the structural stability with cycling was evaluated by Quartz Crystal Microbalance with Dissipation. The results show that Ppy
stabilizes the NP structure avoiding stress features provoked by the formation of -NiOOH. Ppy remains oxidized
during the entire process and, as it is doped with a big counter anion such as dodecylbenzenesulfonate (DBS)
which is not removed during cycling, avoids volumetric changes of Ni(OH)2 leading to higher cyclability.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Nickel hydroxide (Ni(OH)2) is employed in electrochromic devices,
[1] energy storage [2] and electrocatalysis [3]. It exists in two arrangements, and , that can be interconverted in strong alkaline media or
upon electrochemical cycling, causing large volumetric changes that
compromise their performance [4]. In order to stabilize their structures,
approaches such as partial substitution of Ni by other atoms [5,6] and
the preparation of nanostructures [7] have been studied. In this contribution we show that the incorporation of polypyrrole (Ppy) by polymerization of pyrrole (py) in situ during the synthesis of Ni(OH)2
nanoparticles (NPs) stabilizes its badly crystallized phase (bc) [8,9]
along cycling in alkaline media, preventing volumetric changes caused
by the conversion into more opened structures.

The NPs were immobilized on AT-cut 5 MHz piezoelectric quartz

crystals coated with platinum electrodes (Qsense) by electrophoresis
using a Pt counter electrode under an electric eld of 0.5 V cm1. For
the electrochemical characterization, a 0.1 mol L1 KOH solution was
employed as electrolyte and Pt mesh and Ag/AgClKClsat were the counter
and the reference electrodes, respectively. The experiments were
performed with an Autolab PGSTAT30 potentiostat and were concomitantly monitored with a QCM-D (QSense model E4).
For the Attenuated Total Reectance Infrared Spectroscopy (ATRFTIR Bomem MB100) analysis, the NPs were immobilized on a Pt
sheet by casting. The NPs as powder were characterized by X-ray diffraction (XRD Rikagu Miniex) and thermogravimetry (TGA STA
i1500). HRTEM and FESEM images were taken using Jeol Microscopes
(models: JEM 2100 and JSM-7401F respectively).
3. Results and discussion

2. Experimental section
3.1. Structural characterization of Ni(OH)2 nanoparticles
All solutions were prepared in deionized water (UHQ Elga). For the
synthesis of pure Ni(OH)2 NPs, an ultrasonic probe (Sonics Vibra-Cell)
was dipped into a water bath containing a beaker with 10 mL of
0.01 mol L1 Ni(NO3)2 (Aldrich). Then, 200 L of 1 mol L 1 NH4OH
(Synth) was added under 2 s pulsed sonication at 20 W, being maintained for 5 min. For the synthesis of Ni(OH)2/Ppy NPs, the process
was the same but adding 10 L of 0.05 mol L 1 py (Aldrich) and
0.02 mol L 1 of dodecylbenzenesulfonic acid (DBSA Aldrich)
solutions.
Corresponding authors.
E-mail addresses: tania@iq.usp.br (T.M. Benedetti), storresi@iq.usp.br
(S.I. Crdoba de Torresi).

http://dx.doi.org/10.1016/j.elecom.2014.09.012
1388-2481/ 2014 Elsevier B.V. All rights reserved.

Fig. 1(a and b) shows the TEM images of pure and hybrid NPs
(ca. 5 nm in diameter) obtained. The diffractograms of both materials
are nearly identical, being mainly assigned to -Ni(OH)2, with peaks
at 2 = 15.7, 33.2, 38.6, 52.3, 59.3, 62.5, 69.6 and 72.7 [10,11]. However,
peaks assigned to -Ni(OH)2 are also present at 6.5 and 20.7, indicating
an intermediate structure between the well crystallized -Ni(OH)2 and
the disordered -Ni(OH)2. It was conrmed by FTIR where a sharp peak
at 3645 cm1 from the (OH) stretching vibration of the phase, in addition to a broad band centered at 3270 cm1 and a peak at 1640 cm1
assigned to the stretching and bending vibrations of water molecules
from the phase, are observed [12]. The formation of the -Ni(OH)2
phase is observed for reactions at mild temperatures [9,12]. In our

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165

Fig. 1. TEM image of (a) pure Ni(OH)2 and (b) hybrid Ppy/ Ni(OH)2 NPs; (c) Nyquist plots at frequency range from 10 kHz to 10 mHz; amplitude (RMS): 10 mV; E = 0.5 V vs. Ag/Ag+ KClsat.
in 0.1 mol L1 KOH electrolytic solution; (d) mass of electrophoretically deposited NPs as a function of time at electric eld = 0.5 V cm1. () Pure Ni(OH)2 and () hybrid Ni(OH)2/Ppy.

case, the formation of bc structure is explained by the sonication

method that generates high local temperature causing the transition
from to phase [13]. In a previous work, the sonication for 90 min
resulted in phase NPs [14]. In the present case, as a shorter sonication time was employed, the badly crystallized structure was formed.
The high local temperature also generates the radicals H and OH
from water, promoting the polymerization of the py monomer
(Eqs. (1) and (2)) [15,16]. The polymerization reaction is initiated
by the H2O2 formed by combination of two hydroxyl radicals generated by the sonolysis.

H2 O H  OH

OH  OH  H2 O2 :

The TGA results show that pure and hybrid NPs present an initial
mass decrease of 1.8% and 3.7%, respectively, from the removal of
adsorbed water, followed by a large decrease around 250 C of 15.5%
and 18.2% respectively, from the decomposition to NiO [17]. The mass
decrease is higher for the hybrid material, once the polymer decomposition occurs at this same temperature range. Based on this, the weight
percentage of polymer is estimated in approximately 3%. The low
polymer content in the composite explains the reason why the
diffractograms and FTIR spectra of both pure and hybrid NPs are nearly
identical.
3.2. Electrophoretic deposition of the Ni(OH)2 NPs
Due to the incompatibility of the QCM-D with the system employed
for the EPD, the frequency (f) and dissipation (D) changes during the
deposition were measured point to point at different times building
up the frequencydissipation vs. time curves. As D shifts are negligible
with respect to the f changes for harmonics (n) ranging from n = 3 to
n = 11, both lms can be considered rigid [18]. Thus, the mass can be

calculated from the Sauerbrey equation: f = m / CA [19], where

f is the shift in frequency (Hz), m is the mass change (ng), A is the active area of the quartz crystal (0.2 cm2) and C is the mass sensitivity
(17.7 ng cm2 Hz1).
The mass of the lms after 1 h of EPD was 25.2 g cm 2 and
31.4 g cm2 for pure and hybrid NPs, respectively. The higher conductivity of the hybrid material, as demonstrated by impedance measurements (Fig. 1c), leads to a longer time for passivating the substrate
surface due to the EPD process [20], resulting in higher deposited
mass. In fact, the depositing mass change is practically the same at
shorter times being the deviation for lower values observed after
about 20 min of deposition for the pure NPs (Fig. 1d).
From FESEM images (data not shown), no difference in morphology
was observed for both lms. Although the spherical geometry of the
NPs, the lms are brous which was observed in a previous contribution
for V2O5 NPs [21], leading to assume that the lm morphology is associated with the tendency of the NPs to agglomerate into bers under the
applied electric eld.
3.3. Electrochemical/QCM-D characterization
The f and D changes were monitored by QCM-D during the CV experiments. The fn and Dn data were collected from n = 3 to n = 11. As
D 106 shifts are higher than 5% of f shifts in addition to signicant
differences in the values among the different n, the data cannot be converted into mass values using the Sauerbrey equation once viscoelastic
changes are also taking place [18]. Therefore, the f5 data was taken
to evaluate the charge compensation behavior in Fig. 2 being its prole
associated with the ow of species into and out of the lms.
For both materials, in the rst cycles f5 abruptly decreases during
oxidation, being recovered to its initial value upon reduction, in agreement with what was expected for -Ni(OH)2 that loses water molecules
upon reduction due its compact structure [22,23] (Eq. (3)).

NiOH2 OH NiOOH H2 O e :

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F.H.C. Miguel et al. / Electrochemistry Communications 48 (2014) 164168

Fig. 2. j and f5 as a function of E at the 5th cycle (a and d), 20th cycle (b and e) and 50th cycle (c and f) for thin lms obtained from pure (a, b and c) and hybrid NPs (d, e and f);
v = 10 mV s1; electrolyte: KOH 0.1 mol L1 aqueous solution.

For the lm of pure NPs, an inversion of the charge compensation occurs upon cycling, being accompanied by slight dislocation of oxidation
and reduction peaks from 0.53 V to 0.51 V and from 0.30 V to 0.32 V respectively, ascribed to the conversion of -NiOOH into the more opened

-NiOOH that occurs upon overcharge [4], tending to be reduced back to

-Ni(OH)2 with similar lattice structure. The formation of the more
opened structure allows the insertion of both cations and water molecules into the layers [22] (Eq. (4)) and was conrmed by FTIR spectrum
taken after 20 cycles (Fig. 3a).

NiOH2 K ; H2 O OH NiOOHK ; H2 O H2 O e : 4

Fig. 3. FTIR spectra of lms of (a) pure and (b) hybrid NPs before (\) and after () 20
voltammetric cycles at 10 mV s1 in KOH 0.1 mol L1.

On the other hand, for the lms of hybrid NPs, the charge compensation behavior is maintained upon cycling, as well as the oxidation and
reduction peak potentials at 0.50 V and 0.30 V respectively, meaning
that in the presence of Ppy the structure is maintained as corroborated
by the FTIR spectrum taken after 20 cycles (Fig. 3b).
Fig. 4 shows the changes in f and D along time during cycling.
For both cases, initially f is the same for all n and D is relatively low,
meaning that there are no signicant changes in viscoelasticity. The
overall f tends to decrease and its variance tends to increase, as well as
D increases, which can be due to increasing swelling of the lms. This
behavior persists, tending to the stabilization (insets in Fig. 4b and
d) for the lm of hybrid NPs. However, for the lm of pure NPs, f trend
starts to invert from the 7th cycle, being accompanied by a signicant
increase in D (insets in Fig. 4a and c). After about the 40th cycle, the material starts to detach from the substrate, as indicated by the increase of
f. This is associated with signicant volumetric changes caused by phase
transition during cycling.
Based on these observations, we clearly note that Ppy is stabilizing
the NPstructure. At the applied electrochemical window the Ppy is at
its oxidized state during the whole process. The oxidized polymer
prevents the hydroxide layers to be held off, avoiding the conversion
of the -NiOOH into -NiOOH which is associated with volumetric
changes that compromises the lm stability along cycling. In addition,
the DBS counter anion, due to its size, is not removed from the structure [24,25] as observed for small anions that are exchanged by OH
in alkaline solution, compromising the conductivity [26]. The importance of the presence of the big anion is supported by the fact that

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167

Fig. 4. f (a and b) and D 106 (c and d) as a function of t during the 20 rst voltammetric cycles with n = 3 to n = 11 for pure (a and c) and hybrid (b and d) NPs; v = 10 mV s1;
electrolyte: KOH 0.1 mol L1. Insets: data for 100 cycles.

when a small anion such as Cl is employed as counter ion, the resulting

hybrid NP structure is not maintained within cycling (data not shown).
4. Conclusions
We have demonstrated that bc-Ni(OH)2 NP structure is stabilized
by the incorporation of Ppy doped with a large counter ion such as
DBS, that minimizes volumetric changes along cycling, as demonstrated by following structural and viscoelastic changes taking place along
the process. This material can be applied in devices based on Ni(OH)2
where the prevention against mechanical stress due to the -Ni(OH)2/
-NiOOH redox reaction is of crucial importance.
Conict of interest statement
The authors declares no conict interests.
Acknowledgments
Financial support was provided by FAPESP (2009/53199-3) and
CNPq. TMB thanks FAPESP for the fellowship (2012/02117-0).
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