Journal of Colloid and Interface Science 461 (2016) 154–161

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Journal of Colloid and Interface Science

journal homepage: www.elsevier.com/locate/jcis

Microwave-assisted synthesis of simonkolleite nanoplatelets on nickel

foam–graphene with enhanced surface area for high-performance
supercapacitors
S. Khamlich a,b,c,⇑, T. Mokrani d, M.S. Dhlamini c, B.M. Mothudi c, M. Maaza a,b
a
UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk Ridge, PO Box 392, Pretoria, South Africa
b
Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western
Cape Province, South Africa
c
Department of Physics, College of Science, Engineering and Technology, University of South Africa, Private Bag X6, Florida 1710, Johannesburg, South Africa
d
Department of Civil and Chemical Engineering, College of Science, Engineering and Technology, University of South Africa, Private Bag X6, Florida 1710, Johannesburg, South Africa

g r a p h i c a l a b s t r a c t
Nickel foam–graphene (NiF–G) was synthesized by chemical vapor deposition (CVD) followed by a simple microwave-assisted hydrothermal technique to
grow simonkolleite nanoplatelets on the NiF–G to form NiF–G/SimonK electrode for supercapacitor application.

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

Article history: Simonkolleite (Zn5(OH)8Cl2
H2O) nanoplatelets has been deposited on nickel foam–supported graphene
Received 5 August 2015 by using an efficient microwave-assisted hydrothermal method. The three-dimensional (3D) porous
Revised 10 September 2015 microstructure of the as-fabricated nickel foam–graphene/simonkolleite (NiF–G/SimonK) composite is
Accepted 11 September 2015
beneficial to electrolyte penetration and ions exchange, whereas graphene provide improved electronic
Available online 11 September 2015
conductivity. Structural and morphological characterizations confirmed the presence of highly crystalline
hexagonal-shaped nanoplatelets of simonkolleite. Field emission scanning electron microscope (FE-SEM)
Keywords:
of the NiF–G/SimonK composite revealed that the SimonK nanoplatelets were evenly distributed on the
Simonkolleite
Graphene
surface of NiF–G and interlaced with each other, resulting in a higher specific surface area of 35.69 m2 g1
Supercapacitor compared to SimonK deposited directly on NiF 17.2 m2 g1. Electrochemical measurements demon-
Microwave strated that the NiF–G/SimonK composite exhibit a high specific capacitance of 836 F g1 at a current
density of 1 A g1, and excellent rate capability and cycling stability with capacitance retention of 92%
after 5000 charge/discharge cycles.
Ó 2015 Elsevier Inc. All rights reserved.

⇑ Corresponding author at: UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk Ridge, PO
Box 392, Pretoria, South Africa.
E-mail address: skhamlich@gmail.com (S. Khamlich).

http://dx.doi.org/10.1016/j.jcis.2015.09.033
0021-9797/Ó 2015 Elsevier Inc. All rights reserved.
 S. Khamlich et al. / Journal of Colloid and Interface Science 461 (2016) 154–161
1. Introduction
Recently, great research efforts have been made to improve the
energy density, power density and service life of energy storage
devices [1]. Supercapacitors, sometimes referred to as electro-
chemical capacitors or ultracapacitors, bridge the gap between
low power/high energy rechargeable batteries and high power/
low energy electrolytic capacitors due to their high rate capability,
fast charging/discharging rate, long operating lifetimes, high levels
of electrical power and low maintenance cost [2]. In general, super-
capacitors can be divided into two categories of electrochemical
double-layer capacitors (EDLCs) and pseudocapacitor based on
their energy storage mechanism [3,4]. Furthermore, carbon and
transition metal oxides (e.g. CNT [5], carbon aerogel [6], graphene
nanosheets [7], Co3O4 nanowire [8,9], mesoporous NiO [10], RuO2-

xH2O/carbon [11], graphene/SnO2 [12], graphene–MnO2 [13],
V2O5
0.6 H2O nanoribbons [14] and so forth) are the most used
materials for supercapacitors fabrication due to their large surface
area. Lately, graphene has been proven to be an effective material
for supercapacitor electrodes fabrication due to its high electrical
conductivity, high mechanical stability and large surface area
[15,16]. Graphene can be a perfect conductive support, or additive
for electrode materials with pseudocapacitance properties [17].
Metalic nanoparticles [18], nanostructured oxides [19–21] and
conducting polymers [22] were coupled with highly conducting
graphene nanosheets and reduced graphene oxide to improve per-
formance of Li-ion batteries and supercapacitors.
Simonkolleites (Zn5(OH)8Cl2
H2O) nanoplatelets, which possess
a high degree of anisotropy with nanoscale thickness and micro-
length in other dimensions, have attracted tremendous attention
due to their unique morphology associated with prominent physi-
cal and chemical properties and potential applications, such as in
H2 gas sensing and energy storage applications [23–25]. Simonkol-
leite forms hexagonal micro to nanoplatelet crystals with a cleav-
age parallel to the (0 0 1) direction [26]. It is a soft compound
with a Mohs hardness of 1.5 and a specific gravity of 3.2 [23].
The crystal structure of the synthesis analogue of simonkolleite
was reported by Nowacki and Silverman [27] and Allmann [28].
Simonkolleite is electrochemically active due to the existence of
oxygen vacancies on its surface, similar to ZnO nanostructures.
Moreover, the n-type donors nature of these vacancies has a signif-
icant contribution to the material’s conductivity [23]. Due to the
intrinsically lower electronic conductivity and dense morphology
of simonkolleites, great efforts have been made to improve capac-
itive performance of this material with graphene composites
[24,25]. It is worthwhile to mention that, graphene grown directly
on the current collectors by chemical vapor deposition (CVD)
method [29] offers the advantages of binder-free and low contact
resistance, which are important to fabricate the electrodes with
higher specific capacitance and improved power capability.
Low temperature hydrothermal growth of simonkolleites on 3D
NiF–G for electrochemical supercapacitors was reported in our pre-
vious work [24]. The weakness of conventional hydrothermal
aqueous solutions based techniques, typically carried out at low
temperature 90 °C, is the long time scale required for the synthe-
sis. This may lead to defects being introduced in the simonkolleite
nanomaterial and resulting in compromised quality and perfor-
mance to achieve the desired level of energy storage [30]. Despite
being very versatile, hydrothermal aqueous-based reaction sys-
tems for simonkolleites synthesis exhibit a fairly complex relation-
ship between reaction mechanism and reaction parameters
controlling structural morphology. Thus, hydrothermal aqueous-
based synthesis recipe for simonkolleites micro- and nano-
structures demands a high degree of reaction parameter control
to accurately produce the desired structural morphology and
hence high electrochemical performance.
155
As an alternative to hydrothermal aqueous-based synthesis,
microwave-assisted synthesis can significantly decrease the time
required for synthesizing simonkolleites micro- and nano-
structures [31]. Microwave irradiation heats a substance by two
mechanisms, which are dipole polarization and ionic conduction
whereas another called interfacial polarization is a combination
of the two [32]. It shortened reaction time by interacting with
the reaction mixtures on a molecular level leading to an acceler-
ated rate of reaction and hence the growth of the nanomaterial.
And usually a high degree of morphological control during the syn-
thesis of nanostructured materials is achieved by using
microwave-assisted approaches; this technique can also provide
an almost instantaneous and dynamic control over reaction tem-
perature [32].
In this work, we present a simple microwave-assisted
hydrothermal technique to grow simonkolleite nanoplatelets on
a 3D nickel foam–graphene (NiF–G/SimonK) for supercapacitor
application. The NiF–G/SimonK composite has a high spicific elec-
trochemical active surface area and three-dimensionally intercon-
nected networks. The SimonK deposited by the microwave
technique exhibited a nanoplatelets structure uniformly anchored
on 3D porous nickel foam–graphene. The unique structure of the
fabricated NiF–G/SimonK electrode improved ion and electron
exchange in electrochemical processes and also served as a 3D
platform for combination and integration of SimonK on the NiF-
G. The NiF–G/SimonK composite acting as supercapacitor electrode
material displays high specific capacitance, remarkable rate perfor-
mance and prominent cycle stability.
2. Experiments and methods
2.1. Growth of graphene on nickel foam (NiF–G)
Nickel foams (NiF) (Sigma–Aldrich, 450 g1 m2 in bulk density,
95% porositry and 1.6 mm in thickness) were used as the templates
for the CVD growth of graphene and also employed as the current
collector of supercapacitor electrode. The precursor gases were
CH4:H2:Ar. The NiF was annealed at 800 °C in the presence of Ar
and H2 for 20 min in order to reduce the native oxide layer on
the surface of NiF. This process was immediately followed by
CH4 gas introduction at 1000 °C (Fig. 1). The flow rates of the gases
(CH4:H2:Ar) were 10 sccm: 10 sccm: 300 sccm, respectively. After
15 min of growth, the sample was rapidly cooled down to the room
temperature at a cooling rate of 100 °C/min under H2/Ar flow.
2.2. Growth of simonkolleite on NiF–G
An efficient microwave-assisted hydrothermal technique was
used to deposit SimonK nanoplatelets on the NiF–G (Fig. 1). A
25 ml PyrexÒ round-bottom tube was filled with an equimolar
(101 M) aqueous solution of zinc nitrate hexahydrate (Zn(NO3)2

6H2O), hexamethylenetetramine (HMT) and sodium chloride
(NaCl). Subsequently, the NiF–G samples were immersed in the
solution and subjected to microwave irradiation of 700 W under
a pressure of up to 100 bar for 1 h in a single-mode microwave
reactor which is pre-pressurized with N2 gas to prevent boiling
of the solution. The microwave reactor consists of a circular cavity,
containing a waveguide, which delivers single-mode microwaves
for uniform sample heating without any hot or cold spots in the
reaction vessel that are typical for a domestic microwave ovens.
The single-mode microwave cavity is designed to provide a higher
energy density per unit volume of the sample allowing for an effi-
cient preparative chemistry. Thereafter, the microwave reactor was
allowed to cool down to ambient temperature. The final NiF–G/
SimonK composite was obtained after washing and drying. The
156 S. Khamlich et al. / Journal of Colloid and Interface Science 461 (2016) 154–161

Fig. 1. Synthesis process scheme of the NiF–G/SimonK composite.

formation of Zn5(OH)8Cl2
H2O is considered to proceed competi- properties. Hence, in the voltage control (potentiostatic) mode, a
tively in the solution following the successive chemical reaction: small AC voltage of 5 mV (usually 5–50 mV) was applied to disturb
NiF–G/SimonK electrode over a frequency range from 0.01 Hz to
C6 H12 N4 þ 6H2 O ! 6HCHO þ 4NH3 ð1Þ
100 kHz and the current response was measured to obtain the
impedance of the system (the signal of our electrode appeared in
NH3 þ H2 O ! NH4þ þ OH ð2Þ the range from 0.01 Hz to 100 kHz, but for other materials a range
from 0.001 to 3,600,000 could be used). The impedance responses

NaCl þ H2 O ! Naþ þ Cl þ H2 O ð3Þ recorded by the EIS instrument are normally shown as Nyquist
plots that illustrate the relationship between imaginary resistance
ZnðNO3 Þ2
6H2 O þ H2 O ! Zn2þ þ 2NO3 þ 7H2 O ð4Þ or impedance and real resistance or impedance. On the other hand,
the AC voltage used for the NiF–G/SimonK electrode perturbation
 must not cause the system to shift from its equilibrium state. To
5Zn2þ þ 8OH þ 2Cl þ H2 O ! Zn5 ðOHÞ8 Cl2
H2 O ð5Þ
meet this requirement, it is better to measure the EIS of an electro-
Firstly, C6H12N4 decomposes into formaldehyde (HCHO) and chemical capacitor at its open potential voltage (OCV) rather than
ammonia (NH3) (Eq. (1)). Ammonia tends to react with H2O to pro- under load [33].
duce OH- anions (Eq. (2)). Secondly, sodium chloride reacts with
H2O to form sodium cations and chloride anions (Eq. (3)). Further-
more, Zn(NO3)2
6H2O decomposes into zincate ion Zn2+ and nitrate 3. Results and discussions
NO3 (Eq. (4)). Finally, OH and Cl anions react with Zn2+ cations
to synthesize simonkolleite nanoplatelets (Zn5(OH)8Cl2
H2O) (Eq. Fig. 2 shows the X-ray diffraction (XRD) pattern of the fabri-
(5)). cated NiF–G/SimonK electrode. The sharp peak at 2h value of
26.43° indicates high crystallinity and an interlayer space of
0.34 nm of the defect free CVD grown graphene, which is similar
2.3. Material characterization
to the natural graphite but distinct to the commonly used defective
reduced graphene oxide [34]. The strong diffraction peaks at the 2h
The structural characterization of the NiF–G/SimonK composite
values 44.38° and 51.71° are associated with the Ni-foam and are
was investigated by X-ray diffraction (XRD) using a SmartLab
indexed with an asterisk. The diffraction peaks of simonkolleite
(Rigaku) diffractometer with Cu Ka radiation (k = 1.5406 Å),
appear at 2h values of 24.8°, 28.2°, 30.4°, 31.6°, 32.7°, 34.9°,
employing a scanning rate of 0.2° s1 and 2h ranges from 20° to
36.1°, 37.8°, 47.44°, 48.6°, 50.3°, 56.1°, 58.44°, 59.65°, 62.4°,
70°. The Raman analyses were performed using an alpha 300R
66.15°, 67.64° and 68.63°. All these characteristic diffraction peaks
WITec system (WITec GmbH, Ulm, Germany). The excitation
can be indexed to pure rhombohedra simonkolleite structure of
source was a 532 nm laser (2.33 eV, 1 mW power) through a
(0 1 5), (1 1 0), (1 1 3), (1 0 7), (0 2 1), (0 1 8), (0 2 4), (2 0 5), (1 2 5),
numerical aperture of 0.9 and with 100 magnification. A high-
(3 0 0), (0 2 10), (3 0 6), (2 2 0), (2 2 3), (1 3 4), (2 0 14), (1 3 7) and
resolution Zeiss Ultra Plus 55 field emission scanning electron
microscope (FE-SEM) operated at an accelerating voltage of
2.0 kV was used for the morphological investigations of the sam-
ples. Surface area measurements were obtained using the Bru
nauer–Emmett–Teller (BET) method with N2 gas. Pore size and
pore volume were obtained using Barrett–Joyner–Halenda (BJH)
method from the desorption branch of the isotherm. The pore size
distribution was determined by using a desorption isotherm,
assuming a cylindrical pore model via the Barrete–Joynere–Halen
der (BJH) method. The nitrogen adsorption volume at the relative
pressure (P/P0) of 0.994 was used to determine the pore volume
and average pore size. The capacitive properties were investigated
by the cyclic voltammetry (CV) method using an Autolab
PGSTAT302N – High performance workstation (Metrohm Autolab
BV) driven by the NOVA 1.10 software. The as-prepared NiF–G/
SimonK composite served as the working electrode, glassy carbon
rod as the counter-electrode and Ag/AgCl (3 M KCl) as the refer-
ence electrode in 4.0 M KOH electrolyte. Electrochemical impe-
dance spectroscopy (EIS) has an important advantage of using a
very small AC amplitude signals to investigate electrical character-
istics of an electrochemical capacitor without disturbing its Fig. 2. X-ray diffraction pattern of the NiF–G/SimonK composite.
 S. Khamlich et al. / Journal of Colloid and Interface Science 461 (2016) 154–161
(0 4 2) planes, which match well with the standard simonkolleite
peaks (JCPDS No. 07-0155). These simonkolleite peaks are also
similar to those reported in earlier studies [23–25] in which char-
acteristic reflection patterns of the same material were studied.
This confirms a relatively good crystallinity of the simonkolleite
deposited on the NiF–G by using the microwave-assisted
hydrothermal technique.
The structural quality of graphitic materials has been widely
investigated by Raman spectroscopy due to its sensitivity, high
information content, and non-destructive nature [35]. The Raman
spectrum of graphene is usually characterized by three main fea-
tures, the D mode arising from a breathing mode of point photons
of A1g symmetry (1350 cm1), the G mode arising from the first
order scattering of the E1g phonon of sp2 C atoms (usually observed
at 1575 cm1) [36] and the symmetry allowed 2D overtone mode
(2700 cm1). The Raman spectra of NiF–G and NiF–G/SimonK com-
posites were shown in Fig. 3. A broad G and 2D bands were
observed in both samples around 1591 cm1 and 2720 cm1,
respectively. The D band (usually at 1350 cm1), which is attrib-
uted to the disordered graphitic carbon and its intensity, provides
information about the density of defects in the as-grown graphene.
The fact that this band is not visible in the spectrum signifies that
the sample is free of defects. The intensity ratio I2D/IG (0.71) indi-
cates that the as-grown graphene is mainly few-layered (i.e. it has
fewer than five layers) [37]. The Raman peaks around 388, 479 and
727 cm1 indexed by stars, were found to agree very well with
what was reported in the literature (390, 482 and 730 cm1) [38]
for simonkolleite material. A peak at 293 cm1 was attributed to
the Zn–Cl bond stretching vibrations and that at 358 cm1 to
Zn–O which had a vibration characteristic of a simonkolleite struc-
ture. Furthermore, the O–H stretching bands are clearly present at
2962 and 3019 cm1 [38]. Other smaller peaks around 592, 926,
969, 1077, 1154, 1465 and 1776 cm1, also indexed by
stars, result from the contribution of the multiple-phonon scatter-
ing process in the synthesized SimonK nanoplatelets.
Field-emission SEM (FE-SEM) was used in this study to confirm
the morphology of the deposited graphene on NiF and simonkol-
leite nanoplatelets on NiF–G as shown in Fig. 4. It can be seen from
Fig. 4(a) that the 3D Ni-foam is a porous structure (pore size of
0.15–2 mm) with a smooth surface. Fig. 4(b) shows a microimage
of 3D graphene networks grown on Ni foam after the CVD process.
Ripples and wrinkles of graphene were observed on the surface of
Ni foam (inset in Fig. 4(b)) which arises from the different thermal
expansion coefficients of Ni and graphene [39]. Those wrinkles can
provide graphene with a large surface area and good mechanical
Fig. 3. Raman spectra of NiF–G and NiF–G/SimonK composite.
157
properties [39]. The 3D graphene networks grown on Ni foam
was used as templates to construct NiF–G/SimonK electrode for
supercapacitor applications. In the NiF–G/SimonK composite,
nanostructured simonkolleite is densely anchored onto both sides
of the graphene surface (Fig. 4(c)). At higher magnification, it is
observed that the simonkolleite nanostructures are hexagonal
and platelet-like (Fig. 4(d)). The diameter of the simonkolleite
microplatelets is ranging from 200 to 480 nm, and the thickness
is about 20 nm which confirm the nano-nature of the obtained
material.
The specific surface areas and the porous nature of the samples
are determined by measuring nitrogen adsorption–desorption iso-
therms at 77 K (Fig. 5). By comparing the isotherms and pore size
distributions, it can be seen that the isotherm of the NiF–G/SimonK
composite shows a wide hysteresis loop at relative pressure range
of 0.59–1.0P/P0. The corresponding BET specific surface areas are
35.69 m2 g1 and 17.2 m2 g1 for NiF–G/SimonK composite and
NiF/SimonK, respectively. The higher surface area of the NiF–G/
SimonK composite may be attributed to the presence of graphene.
The pore size distribution based on BJH method is confirmed by the
corresponding pore size distributions (the insets of Fig. 5), which
reveals that the existence of mesopores and micropores in the
NiF–G/SimonK composite and NiF/SimonK, with a major pore
diameter of 3.8 nm which further confirms the presence of meso-
porous sites which are used as pathways for transport of ions nec-
essary for power delivery [25]. The supercapacitive performance of
the active electrode material is dependent on its ability to accom-
modate as much active electrochemical sites for charge storage
during operation. The presence of suitable mesopores within the
electrode material is also ideal to ensure the reduction of mass
transfer of electrolyte during fast redox reactions and facilitates
power delivery [25].
SimonK is a promising material for supercapacitors, the use of
NiF–G/SimonK as electrod material has been reported previously
[24,25]. Because of its high specific capacitance, well-accepted
redox behavior, large specific surface area, high conductivity,
high-quality contact interface, and sufficient quantity of active
material, NiF–G/SimonK is expected to be an excellent choice for
electrode materials of supercapacitors. Hereby, simonkolleite
microplatelets, as an example, was deposited on the 3D NiF–gra-
phene network by a conventional-hydrothermal method [24,25].
The conventional electrode fabrication methods requires the poly-
meric binders to stick powder samples to current collectors such as
Ni foam, which decrease the conductivity of the electrode, leading
to a large contact resistance between the active materials and the
current collector [40]. Since the 3D graphene network synthesized
in our experiment is precipitated onto the Ni foam via CVD at a
high temperature, the graphene films possess effective electrical
contact with the Ni foam. Thus, the as-prepared G/SimonK com-
posites on Ni foam can be used for electrochemical testing directly,
without any further treatment.
Cyclic voltammetry (CV) was performed to compare the macro-
scopic electrochemical surface reactions of NiF–G, NiF/SimonK and
the NiF–G/SimonK electrodes at scan rate of 25 mV s1 and a
potential window of 0–0.5 V in 4.0 M KOH electrolyte Fig. 6(a).
NiF–G showed very low intensity current peaks due to the redox
reaction of the NiF in the electrolyte [41], and also to the poor uti-
lization of the available surface area due to the quasi-super
hydrophobicity which is attributed to poor surface wetting [42].
The CV curve of the NiF/SimonK in Fig. 6(a) showed relatively good
electrochemical performance compared to NiF–G, but its CV curve
still has an ill-defined shape. The reason for this could be a
retarded transport of electrolyte ions due to an increase in the par-
ticle size of the simonkolleite owing to aggregation or due to
higher scan rate which induced a fast drop as a result of the high
resistance of the simonkolleite nanoplatelets. Furthermore, a good
158 S. Khamlich et al. / Journal of Colloid and Interface Science 461 (2016) 154–161
Fig. 4. SEM micrographs of (a) bare 3D Ni foam; (b) graphene deposited on Ni foam (c) Simonkolleite deposited on NiF–G; (d) high-resolution image of the simonkolleite
nanoplatelets.
Fig. 5. Nitrogen adsorption–desorption isotherms for NiF–G/SimonK composite and
NiF/SimonK. Inset: corresponding pore size distribution curves.
mirror image with respect to the zero current line was observed in
the CV curve of NiF–G/SimonK electrode with a more rapid current
response on voltage reversal at each end potential. These results
confirmed a superior electrochemical reversibility of the NiF–G/
SimonK compared to NiF/SimonK. This is possibly due to the higher
conductivity of the used graphene that have been entangled with
SimonK nanoplatelets and facilitates the transport of electrolyte
ions during a rapid charge–discharge process. Fig. 6(b) shows the
cyclic voltammograms (CVs) of NiF–G/SimonK at scan rates rang-
ing from 10 to 100 mV/s. As noted, the CV curves present a pair
of large redox peaks which corresponds to the intercalation and
deintercalation of K+ from the electrolyte into SimonK [24]. This
clearly demonstrates that the charge storage mechanism is mainly
ascribed to the pseudocapacitance resulted from the faradaic pro-
cesses of the high specific surface area of 3D porous surface mor-
phology. The anodic and cathodic peaks of the CV curves show a
nearly symmetric characteristics, suggesting a high redox
reversibility of the microwave assisted hydothermal synthesized
simonkolleite nanoplatelets. Although the redox transformation
is similar at different scan rate, after a careful comparison, it can
be found that, at higher scan rate, the anodic peak of CV curve is
relatively sharper, implying a fast charge-transfer process and
good redox reversibility, which are believed to be the two critical
factors for high performance supercapacitors.
Fig. 6(c) shows the first discharge curves of NiF–G/SimonK at
galvanostatic current densities of 1, 2.5, 5, 7.5 and 10 A g1 in the
potential range of 0–0.5 V. A pseudocapacitance characteristic
was observed from the shape of the discharge curves, this was in
agreement with the results of the CV test. The appeared potential
plateaus at around 0.22 V in discharging processes is correspond-
ing to the cathodic peaks in the CV curve. This potential plateaus
result from the exchange of electrons during the oxidation or
reduction of the active material. The specific capacitance can be
calculated according to the following equation [25]:
I  Dt
C¼ ð6Þ
m  DV
where C (F g1) is the specific capacitance, I (mA) the discharge cur-
rent, Dt (s) the discharging time, DV (V) represents the potential
drop during discharge process, and m (mg) the mass of the active
material used in the electrode. By using the Eq. (6), higher values
of the specific capacitance calculated from discharge curves for
NiF–G/SimonK were found, 836, 748.1, 639, 582.3 and 520 F g1
at 1.0, 2.5, 5.0, 7.5 and 10 A g1, respectively. The capacitance grad-
ually decreases as the current density increases. The reason is that
at a higher current density the incremental voltage drops and the
active material involved in the redox reaction is insufficient [42].
This confirmed that the SimonK deposited on NiF–G using the
microwave assisted hydrothermal synthesis method, possesses a
high and stable specific capacitance at high charge/discharge rates
compared to the SimonK deposited by a conventional hydrothermal
method 164 F g1 at 10 A g1 [24], which is very important for elec-
trode materials of supercapacitors to provide a high power density.
 S. Khamlich et al. / Journal of Colloid and Interface Science 461 (2016) 154–161 159

Fig. 6. (a) CV curves of NiF–G, NiF/SimonK and NiF–G/SimonK composites at a scan rate of 25 mV s1 in 4.0 M KOH electrolyte; (b) CV curves of the NiF–G/SimonK composite
electrode at different scan rates; (c) galvanostatic charge–discharge curves of the NiF–G/SimonkK composite at different current densities; (d) Nyquist plot of the NiF–G/
SimonK composite – the inset in (d) shows the magnified plots in the high-frequency region.

Potentiostatic electrochemical impedance spectroscopy (EIS)

measurements were performed to further characterize the perfor-
mance of NiF–G/SimonK. Potentiostats are required to run impe-
dance tests in a linear regime, so that test results remain
consistent throughout [43]. The Nyquist plot of the NiF–G/SimonK
electrode is shown in Fig. 6(d). The intercept on the X-axis in the
high frequency region represents the intrinsic ohmic resistance
of the internal resistance or equivalent series resistance (ESR) of
the electrode material and the electrolyte [44]. The ESR value that
was obtained from Fig. 6(d) for the NiF–G/SimonK electrode was
1.95 X in 4 M KOH aqueous electrolyte, which is less than that of
the SimonK deposited on NiF–G by a conventional-hydrothermal
method (2.1 X) [24]. At low frequency, the impedance plot should,
theoretically, be a vertical line parallel to the vertical Z00 axis. The
observed tilted vertical line indicates a good capacitive behavior
of the simonkolleite material and a relatively lower diffusion resis-
tance of ions within the structure of the fabricated NiF–G/SimonK
electrode [25].
Fig. 7. Cycle performance of the NiF–G/SimonK composite at the current density of
The stability and service performance of the fabricated NiF–G/ 10 A g1 in 4.0 M KOH solution. The inset shows the charge–discharge profile for
SimonK electrode is crucial for practical use in supercapacitor the NiF-G/simonkolleite composite.
applications. In this regards, a cycling stability at high current den-
sity was performed. As shown in Fig. 7, a 92% of the initial specific
capacitance remains after 5000 continuous charge–discharge electrical conductivity of the used graphene and the enhanced
cycles at the high current density of 10 A g1. This is a confirmation specific surface area by the efficient microwave-assisted growth
that the fabricated NiF–G/SimonK electrode material has a much of simonkolleite nanoplatelets on NiF–G, allowing fast and effec-
higher degree of charge–discharge reversibility and a long tive ion charge transfer and electron transport. In order to confirm
term electrochemical stability. The excellent pseudocapacitive the structural stability of the fabricated electrode, Raman analysis
properties and high cycling stability can be attributed to the high for NiF–G/SimonK was performed after 5000 cycles as shown in
160 S. Khamlich et al. / Journal of Colloid and Interface Science 461 (2016) 154–161
Fig. 8. Raman spectra of NiF–G/SimonK as-deposited and after 5000 cycles.
Fig. 8. The relative D-, G- and 2D-peaks of graphene heights change
noticeably for the cycled NiF–G/SimonK electrode. The D-band
intensity increases substantially, the G- increased significantly
and the 2D-band decreased slightly. These results revealed some
degree of degradation in the graphene after the cycling. Moreover,
the Raman spectral of NiF–G/SimonK anode (Fig. 8) clearly displays
a decrease in SimonK peaks, which might be results of formation of
a solid electrolyte interface (SEI) on the surface of SimonK nanopla-
telets. These results confirmed that the active material electrode
still reveals outstanding structural stability which contributed to
its good electrochemical and cycling stability.
4. Conclusion
Simonkolleite (SimonK) pseudocapacitive active material with
nanoplatelets structure have been successfully deposited on nickel
foam–graphene (NiF–G) by an efficient microwave assisted
hydrothermal synthesize method. Morphological investigation of
the fabricated NiF–G/SimonK composite revealed that the SimonK
nanoplatelets were evenly distributed on the surface of NiF–G and
interlaced with each other, resulting in a higher specific surface
area of 35.69 m2 g1 compared to SimonK deposited directly on
NiF 17.2 m2 g1. Furthermore, electrochemical measurements
demonstrated that the NiF–G/SimonK composite exhibit a high
specific capacitance of 520 F g1 at a current density of 10 A g1,
This confirmed that the SimonK deposited on NiF–G using the
microwave assisted hydrothermal synthesis method, possesses a
high and stable specific capacitance at high charge/discharge rates
compared to the SimonK deposited by a conventional hydrother-
mal method 164 F g1 at 10 A g1. The electrode material also exhi-
bits excellent performance and long-term cycling stability which is
due to efficient charge transfer and ion diffusion in the porous net-
work of the composite. This results confirmed that graphene play
an important role in a long-term cycling stability of the electrode
and showed that the microwave assisted hydrothermal synthesize
method has an advantage over the conventional hydrothermal syn-
thesis of SimonK nanoplatelets for supercapacitors applications.
Acknowledgements
This work was sponsored by the UNESCO UNISA Africa Chair in
Nanosciences & Nanotechnology and the Nanosciences African
Network (NANOAFNET), by the physics department of the Univer-
sity of South Africa (UNISA). A special thanks to the team of the
chemical engineering departments of UNISA for assisting us with
the electrochemical characterisations.
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