Electrochimica Acta 184 (2015) 193–202

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Synthesis and characterization of Nitrogen-doped & CaCO3-decorated

reduced graphene oxide nanocomposite for electrochemical
supercapacitors
Zafar Khan Ghouria,b , Nasser A.M. Barakatb,c,* , Al-Mahmnur Alama,b ,
Mohammad S. Alsoufid , Tahani M. Bawazeere, Ahmed F. Mohamedd,f , Hak Yong Kima,b,**
a
Advanced Materials Institute for BIN Convergence, Department of BIN Convergence Technology, Chonbuk National University, Jeonju 561-756, Republic of
Korea
b
Department of Organic materials and Fiber Engineering, Chonbuk National University, Jeonju 561-756, Republic of Korea
c
Department of Chemical Engineering, Faculty of Engineering, El-Minia University, El-Minia, Egypt
d
Department of Mechanical Engineering, Collage of Engineering and Islamic Architecture, Umm Al-Qura University, Makkah, Saudi Arabia
e
Department of Chemistry, Faculty of Applied Sciences, Umm Al-Qura University, Makkah, Saudi Arabia
f
Department of Mechanical Engineering, Collage of Engineering, Sohag University, Sohag, Egypt

A R T I C L E I N F O A B S T R A C T

Article history: Alone, it is expected, and also was experimentally proved, that calcium carbonate and reduced graphene
Received 14 July 2015 oxide do have negligible specific capacitance due to the chemical composition of both materials.
Received in revised form 14 October 2015 However, synthesis of CaCO3 on the form of very thin sporadic layer attaching rGO results in dramatic
Accepted 14 October 2015
increase in the specific capacitance of the obtained composite due to formation of the electrochemical
Available online 17 October 2015
double layer at the interfacial area. Moreover, the specific capacitance could be further enhanced by
nitrogen-doping of the rGO sheets. Typically, a novel N-rGO/CaCO3 composite has been successfully
Keywords:
synthesized by heat reflux strategy with graphite powder, calcium acetate and urea as raw materials.The
Supercapacitors
Nitrogen-doped graphene
composite was characterized by X-Ray diffraction (XRD), high resolution transmission electron
Calcium Carbonate microscopy (HR-TEM), field-emission scanning electron microscopy (FESEM), coupled with rapid EDAX
graphene composites (energy dispersive analysis of X-Ray) and X-ray photoelectron spectroscopy. The utilized physiochemical
characterizations indicated that the final prepared composite can be demonstrated as N-doped rGO
decorated by very thin discrete layer from calcium carbonate. Supercapacitive performance of N-rGO/
CaCO3 composite has been investigated by cyclic voltammetry (CV), galvanostatic charge-discharge and
electrochemical impedance spectroscopy in 1 M KOH solution. The results reveal that the N-rGO/CaCO3
composite delivers a large specific capacitance of as high as 214 Fg
1 and 188 Fg
1 at 5 mV s
1and
1.0 Ag
1, according to CV and galvanostatic charge-discharge tests, respectively; while the CaCO3, rGO,
rGO/CaCO3, N-rGO based electrodes has a poor electrochemical performance at the same conditions.
Moreover, the as-prepared composite exhibited excellent long cycle stability with about 88.7% specific
capacitance retained after 10,000 cycles.
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction alternative environmentally friendly sources of energy [1–3].

Expected depletion of the natural resources and serious
environmental condition are driving the researchers to identify
* Corresponding author at: Chonbuk National University, Department of Organic
materials and Fiber Engineering, Jeonju 561-756, Republic of Korea.
Fax: +82 632702348.
** Corresponding author at: Chonbuk National University, Advanced Materials
Institute for BIN Convergence, Department of BIN Convergence Technology,
561-761, Republic of Korea. Tel.: +82 632702351; fax: +82 632704249.
E-mail addresses: nasser@jbnu.ac.kr (N.A.M. Barakat), khy@jbnu.ac.kr
(H.Y. Kim).
Supercapacitors, also known as electrochemical capacitors, are one
of the auspicious electrochemical energy storage devices due to
their high power characteristics compared to batteries, high
energy density compared to conventional capacitors, long cycling
life and short charging time [3–7].
There are two energy storage mechanisms involved in the
supercapacitors. The first one is related to separation of electronic
and ionic charges at electrode/electrolyte interface and it is called
the electrochemical double-layer capacitors (EDLC). Various
carbon-based materials such as carbon nanotubes (CNTs) and
activated carbon (AC) have been considered for use as the

http://dx.doi.org/10.1016/j.electacta.2015.10.069
0013-4686/ ã 2015 Elsevier Ltd. All rights reserved.
194 Z.K. Ghouri et al. / Electrochimica Acta 184 (2015) 193–202
electrodes material in EDLC capacitors [3,8–12]. While,the second
one involves absorption or insertion of electro-active species into
solid phase accompanied by charge transfer processes, this kind is
called pseudocapacitors; numerous metal oxides such as SnO2,
MoO3, RuO2, and MnO2, and electronically conducting polymers
have been used to enhance specific capacitance via pseudocapa-
citive redox reactions [3,13–19]. As aforementioned, most of the
invoked metals were utilized in the oxide form which can be more
sensitive to the chemicals compared to some inorganic groups
such as carbonate.
Although, alkaline earth metal-based compounds (e.g. CaCO3)
are abundant and cheap materials, exploiting of these materials in
supercapacitors application is very rare. Calcium carbonate has
three different anhydrous polymorphs forms such as hexagonal
b-CaCO3 (calcite), orthorhombic l-CaCO3 (aragonite), andm-CaCO3
(vaterite) [20]. Thermodynamically, the moststable form of CaCO3
under normal conditions is hexagonal b-CaCO3 (calcite), aragonite
and vaterite are not stable, but they transform into the stable
calcite [21].
Carbon-based supercapacitors revealed outstanding capaci-
tance performance due to their high surface area and high
electrical conductivity [22]. Single- and few- layer graphenes have
gained much prominence in the recent years due to the heightened
awareness of their potential applications in lithium secondary
batteries, nanoelectronics and supercapacitors [23–25]. However,
most of the electronic applications are handicapped by the absence
of a bandgap in the inherent material [26,27]. It becomes necessary
to tune the band gap in graphene, in this regard numerous
methodologies have been developed to enhance the semiconduct-
ing properties demonstrated by creating confined geometries of
quantum dots [28], nanomesh [29], nanoribbons [30], but one of
the most feasible methods to control the semiconducting
properties of graphene is by doping with elements such as
nitrogen and boron, which is a process deliberately used to tailor
the electronic and electrochemical properties of graphene.
Nitrogen atom can modify the electronic band structure of
graphene significantly by open up an electronic bandgap between
valence and conduction bands. There are different approaches of
doping of graphene with heteroatoms such as solvothermal
synthesis [31], pyrolysis of graphene oxide with melamine [32],
gas phase synthesis [33], plasma reaction [34], wet chemical
reaction of graphene oxide with dicyandiamide [35] and CVD
based synthesis [34,36].
Thus the objective of this research is to combine the merits of
nitrogen-doping and CaCO3-incoporation for the reduced gra-
phene oxide in order to introduce a beneficial use of the prepared
composite in supercapacitors applications. In this article, we report
a promising and low cost synthesis of nitrogen/CaCO3/reduced
graphene oxide nanocomposite by simple heat reflux technique;
moreover the synthesis technique was efficient, green and cost
effective with nitrogen doped graphene and CaCO3 nano composite
formed in one step.
The electrochemical measurement was carried out in aqueous
KOH, because the KOH electrolyte has low resistivity and high
stability compared to H2SO4 electrolyte. Moreover, the KOH solution
also shows good performance at low and high temperature.
Interestingly, electrochemical tests showed that the introduced
nanocomposite electrode exhibited a high specific capacitance
and an excellent rate discharge performance in 1 M KOH solution.
2. Experimental
2.1. Materials
Natural graphite powder, Calcium acetate monohydrate
(CaAc, 99 %) and Hydrazine monohydrate (98%) were bought
from Sigma-Aldrich, USA. Urea (Ur, 99 %), Sulfuric acid (99%),
hydrochloric acid, hydrogen peroxide, were purchased from
Samchun Pure Chemical Co., Ltd. (Korea). Potassium permanganate
(Junsei Chemical Co., Ltd., Japan) was used as an oxidizing agent.
All the chemicals were used without any further purification.
2.2. Preparation of Graphene Oxide (GO)
The modified Hummers method [37] was used to oxidize
natural graphite powder to prepare graphene oxide (GO) in a
distinctive synthesis. Typically, 100 ml of sulphuric acid (concen-
trated) was taken in a reaction flask (round bottom flask which
contains a magnetic stirring bar and thermometer) which was
previously cooled by immersion in an ice bath for 30 min. Then
4 gm of natural graphite powder was added into the reaction flask
with vigorous stirring to avoid agglomeration and obtaining a
homogeneous dispersion. Subsequently, 12 g of potassium per-
manganate was added gradually over 20 to 30 min, to the above
mixture with stirring for 2 h at a constant temperature of 0 to
5  C.After dilution with 150 ml DI water, the temperature was
increased to 98  C, followed by stirring for another 1 h. About 45 mL
(30 wt. %), H2O2 was added until the color changed and left over
night at room temperature. Finally the mixture was filtered and
washed several times with 5% HCl and deionized water until no
manganese salt in the filtrate was detected. The prepared GO was
suspended in water to give a brown dispersion and was subjected
to repeat washing with DI water to completely remove residual
salts and acids and finally precipitate was filtered and then the
solid was dried in vacuum oven at 60  C for 24 h.
2.3. Preparation of Nitrogen doped reduced graphene oxide and CaCO3
Composite(N-rGO/CaCO3)
The N doped rGO and CaCO3 composite was synthesized by
reflux method. In a typical procedure, about 62.5 wt % of GO was
exfoliated in 250 mL distilled water by ultrasonication for 60 min in
a water bath. About 6.25 wt%, calcium acetate (CaAc) and 31.25 wt%
urea (Ur) was dissolved in 50 ml of DI water. The mixture was
stirred for 3 h at 60  C, and then 200 mL hydrazine monohydrate
98% was added to the supernatant mixture. The resulting
suspension was then refluxed at 150  C for 5 h. After the suspension
was cooled down to room temperature, the final product was
collected by filtration and washed with 1000 ml distilled water,
and dried in vacuum at 60  C for 24 h.
2.4. Preparation of working electrode
Preparation of working electrode was carried out by mixing
2 mg of the nanocomposite, 20 mL of Nafion solution (5 wt. %) and
400 mL of isopropanol. The slurry was sonicated for 30 min at room
temperature. The ultrasonically dispersed nanocomposite (15 mL)
was spread by micro pipette on to the active area of the glassy
carbon electrode which was then subjected to drying process at
80  C for 20 min [1–3].
The active zone of the utilized glassy carbon electrode was a
circle with a diameter of 3 mm. Therefore, the active area was
estimated (0.0713 cm2) and all the data was normalized to this
area.
2.5. Characterizations
The characterization experiments were carried out at room
temperature. The phase and crystallinity of the N doped rGO and
CaCO3 nanocomposite were characterized by X-ray diffractometer
(XRD, Rigaku, Japan) with Cu-Ka (l = 1.54056 Å) radiation operat-
ing at 45 kV and 100 mA over a range of 2u angle from 10 to 80 ,
 Z.K. Ghouri et al. / Electrochimica Acta 184 (2015) 193–202
scanning at a rate of 4 /min. The morphology, crystalline size, and
crystal structure of the samples were determined by field-emission
scanning electron microscopy (FESEM, Htachi S-7400, japan)
coupled with rapid EDAX (energy dispersive analysis of X-Ray)
analysis for composition and distribution of elements with the
incident electron beam energies ranging from 3 to 30 KeV, which
impinges the sample surface from the normal angle. TEM, High
resolution TEM images and selected area electron diffraction
patterns were observed by JEOL JEM-2200FS transmission electron
microscope (TEM) operating at 200 kV equipped with EDX (JEOL,
Japan). The surface of the sample was characterized by X-ray
photoelectron spectroscopy (XPS) using a PHI-1600ESCA electron
system (America PE Company) with Al Ka (1486.6 eV) radiation.
2.6. Electrochemical measurements
The electrochemical measurements were carried out inconven-
tional three electrode electrochemical cell (VersaSTAT 4, USA) at
room temperature in a 1 M KOH solution. A glassy carbon electrode
made in the above mentioned procedure used as a working
electrode while Pt wire and an Ag/AgCl electrode were used as the
auxiliary and reference electrodes, respectively.All potentials were
quoted with regard to the Ag/AgCl electrode. Normalization of the
current density was achieved based on the surface area of the
utilized glassy carbon electrode (0.0706 cm2).
3. Results and Discussion
Among the various analytical techniques, X-ray diffraction is
one of the most important characterization tools used in solid state
chemistry and materials science to investigate the fingerprint
characterization of the crystalline materials and the determination
of their structure. The representative XRD pattern of the N-rGO/
CaCO3 nanocomposite powder is presented in Fig. 1. As shown, the
strong diffraction peaks at 2u values of 20.9 , 25.9 , 42.6 and 77.7
corresponding to (0 11), (111), (0 2 2) and (2 2 5) crystal planes,
respectively indicate formation of l-CaCO3 and characterizing this
support as a crystalline carbonate with a orthorhombic Aragonite
structure [space group: Pnma (62)] according to the JCPDS No: 98-
016-9912 with lattice constants a = 5.846 Å, b = 4.978 Å, c = 8.053 Å;
a = b = g = 90. Easy and trustable differentiation between graphite,
GO and graphene can be carried out by using XRD analysis. For
instance, the graphitic structure is assigned by a sharp peak at 2u of
26.5 ((0 0 2) crystal plan) [38]. After oxidation to GO, a new
Fig. 1. XRD pattern of as-synthesized N-rGO/CaCO3 nanocomposite.
195
diffraction peak appears at 2u of 10.5 , along with the disappear-
ance of the graphite peak [38]. However, graphene is identified by a
broaden peak at 2u of 27.5 [39,40] which indicates small
crystalline size of graphene in single or few layers structure.
Accordingly, due to absence of GO representing peak and having a
broad peak within the range of graphite and rGO standard peaks, it
can be claimed that XRD supports formation of rGO because all the
other characterization affirmed the exfoliation.
The morphologies or topographic details of the introduced
nanocomposite were investigated via field emission scanning
electron microscopy (FESEM). As shown in Fig. 2(a) graphite could
be successfully converted to rGO consisting of large number of thin
curled and corrugated sheets with two dimensional porous
conductive network structure which is advantageous for the fast
collection and conduction of electrons during the charge-discharge
process, Fig. 2(b) shows the cross sectional view of the prepared
composite, we can see that the surface of the nanosheets are
wrinkled and rough; moreover, allied and closely associated with
each other.
The elemental composition of the as-prepared nanostructure
was studied by EDX and elemental mapping. A particular area of
the EDX spectrum from Fig. 2(c) was taken, and the result is
established in Fig. 2(d). The analysis revealed the existence of
calcium (Ca), oxygen (O), carbon (C) and nitrogen corresponds to
the well-defined peaks, no other peaks related with any other
impurities were detected in the spectrum which clearly conformed
that the prepared nanomaterials are purely made by Ca, C, O and N.
To check the distribution of Ca, O, C and N, elemental mapping
of the specific area shown in Fig. 2(e) was carried out, and the
results are represented in Fig. 2(f–i). The examination shows that
Ca, O, C and N are evenly distributed over the entire material,
which further clearly confirmed that the CaCO3 are well dispersed
onto the surface of rGO.
In order to obtain comprehensive analysis on the crystallinity
and morphology, the prepared composite was identified by TEM
and SEAD analyses. Normal TEM images of N-rGO/CaCO3 sample
show wrinkled and ultrathin transparent graphene nanosheets
resulted from the exfoliation of graphite. Also, it was observed as
thin nanosheets with some folded area; this was credited to the
stacking of numerous dissimilar pieces of graphene as the effect of
strong p-p stacking interaction on the graphene surface as
presented in Fig. 3(a). In addition, a high-resolution TEM (HR-TEM)
image of N-rGO/CaCO3 nanomaterial edges provides the cross-
sectional view shown in Fig. 3(b & c), Indicate that the thickness of
the composite is similar to 4–5 layers. The red arrows and circles in
the HR TEM image (Fig. 3(c & d)) point to various crystalline thin
layers attaching the amorphous rGO support. As XRD pattern
confirms presence of CaCO3, so these crystalline spots can be
assigned to the inorganic counterpart in the introduced composite.
The SAED pattern of N-rGO/CaCO3 electrode is shown in the inset
(Fig. 3(b). The diffraction spots of the nanocomposite clearly
showed well resolved lattice fringes and diffraction cycles,
indicating the high crystalline nature of the attached CaCO3 layers.
TEM line EDX analysis was performed to understand the
composition of the formed composite, as shown in the main
panel (Fig. 3(e)), the attached calcium carbonate layers have large
areas. Accordingly, uniform elemental distribution can be observed
for the detected elements (Ca, C, O and N) along with randomly
selected line. Overall, from normal TEM results, it can be claimed
that the formed CaCO3 does not form observable nanoparticles
decorating the graphene sheets; instead, as shown in the HR TRM
(Fig. 3C&D), the metallic compound is deposited in very thin
discrete layers on the rGO surface which was marked by the red
arrows and circles. Moreover, elemental mapping (Fig. 2E to 2H)
and line TEM-EDX (Fig. 3E) results reveal that calcium is uniformly
distributed on the surface of the produced graphene which
196 Z.K. Ghouri et al. / Electrochimica Acta 184 (2015) 193–202

Fig. 2. (a and b) FESEM analysis of as-synthesized N-rGO/CaCO3 nanocomposite (c and d) SEM images with corresponding EDS maps for Ca, C, O, and N (e) elemental maping
of as-synthesized N-rGO/CaCO3 nanocomposite.

confirms the aforementioned hypothesis about formation of rGO
decorated with very thin discrete layer from CaCO3.
XPS analysis was carried out to quantify the surface composi-
tion and the valence state of the prepared N-rGO/CaCO3 composite.
The corresponding spectrum of prepared N-rGO/CaCO3 composite
is shown in Fig. 4(a). The survey scan indicates the existence of C, O,
N and Ca elements. Presence of N1s and O1s peaks laying at 401 eV
and 532 eV, respectively indicated presence of N and O. The
observed C1s peak is accredited to graphene; however the peak at
348 eV (Ca2p) confirms the presence of Ca. The atomic elemental
percentage of carbon, nitrogen, oxygen and calcium are summa-
rized in the inset in Fig. 4(a). The de-convolution of Cs1 regions of
the spectrum for the identification of the surface functionalities
are shows in Fig. 4 (b) and fitted by five main peaks. The peaks at
284.6, 287.7, 289.1 and 291 eV were assigned to

C

C

/


C¼C

,

C¼O,

COOH and p-plasmon generated from p-p*
shake-up transitions, respectively. However, the appearance of a
peak at 285.6 eV reflects the bonding between carbon and nitrogen
 Z.K. Ghouri et al. / Electrochimica Acta 184 (2015) 193–202 197

Fig. 3. (a) TEM image of as-synthesized N-rGO/CaCO3 nanocomposite (b-d) HRTEM image, the inset in panel B displays SEAD image and (e). Line TEM EDX analysis of as-
synthesized N-rGO/CaCO3 nanocomposite. The red arrows in panel C and red circles in panel D point to the thin CaCO3 crystalline layer.

atoms as

C¼N

conforming a successful reduction of GO and
doping N into to graphitic layer of graphene [41]. According to the
N 1s spectrum (Fig. 4(d)), three types of doping N, including
pyridinic nitrogen (398.1-399.3 eV), pyrrolic nitrogen (399.8-
401.2 eV) and quartenary nitrogen (401.1-402.7 eV) can be
detected. The peak position of these nitrogen types varies in a
relatively wide range in different studies [42,43]. The big variance
of the peak locations of nitrogen configurations may be due to the
different environments of nitrogen [44], Apart from above
mentioned nitrogen types, peak corresponding to N-oxides of
pyridinic N is also detected at 402.8 eV [45,46]. From the N 1s
spectra, the nitrogen content was found to be 3.24 at. %. Fig. 4(f)
clearly shows the content proportion of different N

bonding
configuration in synthesized composite. The O1s spectra of the
composite in Fig. 4(c) confirms the presence of some C

O

C and
N

O

C functions at 531.5 eV, 533.3 eV, respectively [47–50]
while Ca2p spectra of the composite in Fig. 4(e) exhibits two
distinguished peaks of Ca 2p3/2 and Ca 2p1/2 at 347.3 and
350.9 eV, respectively. Considering the XPS data which gave solid
proof about doping of the prepared rGO by nitrogen atoms, the
final prepared composite can be demonstrated as N-doped rGO
decorated by very thin discrete layer from calcium carbonate.
To investigate the significance of decorating rGO by the
electrochemically inert CaCO3 layer as well as the role of nitrogen,
the electrochemical performance of pristine CaCO3 nanoparticles,
rGO, rGO/CaCO3, N-rGO and N-rGO/CaCO3 as electrode material
198 Z.K. Ghouri et al. / Electrochimica Acta 184 (2015) 193–202

Fig. 4. (a) XPS spectra survey of as-synthesized N-rGO/CaCO3 nanocomposite (b) C1s spectra (c) O1s spectra (d)N1s spectra (e) Ca2p spectra of as-synthesized N-rGO/CaCO3
nanocomposite and (f) The content of three nitrogen species in N-rGO/CaCO3 nanocomposite.

was evaluated. Cyclic voltammetry (CV) analyses were carried out
in three-electrode system using 1 M KOH solution. Relative CV
curves for the investigated electrodes at various scan rates ranging
from 5 to 1000 mV/s are shown in Fig. 4(a-e). The specific
capacitance (Csp, Fg
1) from the CV curves were calculated
according to the following integral equation [51].
Z negligible specific capacitance (about 1.0 F/g at 5 mV s
1). Fig. 5
1
C sp ¼ IðVÞdV  ð1Þ
2m:u:DV
Here, Csp is the specific capacitance, m is the mass of the grafted
composite, u is the potential scan rate, DV is the sweep potential
window and I (V) is the voltammetric current on CV curves, A is the
geometric area of the electrodes respectively.
The CV curves of the CaCO3 electrode at different scan rates as
shown in Fig. 5(a) exhibit a non-rectangular shape with various
prominent redox peaks appeared at -0.2 to 0.3 V, reflecting tinny
pseudo-capacitance behavior. CaCO3 based-electrode showed
(b) shows the CV curves of rGO electrode at different scan rates.
The current densities for the rGO electrode increased slightly
compared to those for the pristine CaCO3 electrode and exhibit a
rectangular shape without obvious redox peaks showing
 Z.K. Ghouri et al. / Electrochimica Acta 184 (2015) 193–202 199

Fig. 5. Cyclic voltammograms of as-synthesized nanocomposite (a) CaCO3, (b) rGO, (c) rGO/CaCO3, (d) N-rGO and (e) N-rGO/CaCO3 in 1 M KOH solution at different scan rates.
Figure.6. (a) Effect of scan rate on specific capacitance, (b) EIS spectrum of CaCO3,rGO, rGO/CaCO3, N-rGO and N-rGO/CaCO3 electrode.

electrochemical double layer (EDL) capacitance rather than pseudo
capacitance due to the oxygen functionalities; its corresponding
capacitance reached to 5.7 Fg
1 at 5 mV/s. In contrast, the CV
curves of rGO/CaCO3 and N-rGO (Fig. 5(c & d)) had similar
rectangular nature; however, the area covered by CV curves was
more than that of pristine CaCO3 and rGO. The corresponding
specific capacitance of rGO/CaCO3 and N-rGO electrodes were
found to be 61.6 and 89.6 Fg
1, respectively. Compared to the
CaCO3, rGO, rGO/CaCO3 and N-rGO electrodes, remarkable increase
in electrochemical area and current density was obtained for
N-rGO/CaCO3 electrode (Fig. 5(e)). Moreover, current density
increased gradually with scan rate indicating a surface-confined
electrochemical process [52]. The specific capacitance deduced
from CV curves of the N-rGO/CaCO3 electrode was found to be
214 Fg
1 at 5 mV/s.
Fig. 6(a) shows the comparative study of the specific capaci-
tance at different scan rate for the 5 types of electrode materials.
Numerical integration model was established to estimate the
200 Z.K. Ghouri et al. / Electrochimica Acta 184 (2015) 193–202
Fig. 6. (a) Effect of scan rate on specific capacitance, (b) EIS spectrum of CaCO3, rGO, rGO/CaCO3, N-rGO and N-rGO/CaCO3 electrode.
specific capacitance at every scan rate as follows [51]
ðV nþ1
V n Þ  ðInþ1 þ In Þ=ðV nþ1 þ V n Þ
Where, N is the number of points in CV cycle. The pristine CaCO3
and rGO electrode have good rate capability with very low specific
capacitance, while N-rGO and rGO/CaCO3-based electrodes exhibit
much higher specific capacitance with a poor rate capability
compared to the pristine CaCO3 and rGO-based electrodes.
However, N-rGO/CaCO3 nanocomposite based electrode exhibits
very high specific capacitance and shows some dependency on the
potential scan rate, proposing that the accessibility of the
electrolyte to the electrode in not so good, and only the external
sites can take part in ion transfer reaction at high scan rate. At
lower scan rates, the entire active surface (external and internal)
can be utilized for the electrochemical utilization of the proposed
nanocomposite.
From the obtained results in Fig. 5 and the estimated specific
capacitance results in Fig. 6A, it is clear that both of rGO and CaCO3
nanoparticles have very low specific capacitance, however
combination the two compounds reveals to produce a composite
having distinctly high specific capacitance. The observed low
specific capacitance in the pristine materials is understandable
because both materials cannot form the electric double layer (EDL)
as they composed of either a single metal (e.g. carbon in case of
rGO) or an ionic compound (CaCO3). Moreover, both materials are
chemically stable in the alkaline medium so no chance to form
distinct redox reaction; pseudo specific capacitance. However, and
specifically because of the obtained structure in which CaCO3 is
formed in the form of thin discrete layer attaching the carbon
sheets, there is a good chance to form the EDL.In more details, due
to presence of excess electrons in the carbonate group, it can form a
Van der Waal force with the rGO sheet. Accordingly, under applied
voltage, an EDL can be formed which results in having the observed
high specific capacitance. Therefore, it can be claimed that the
obtaining CaCO3 in the form of the observed discrete layer
enhances the specific capacitance of the composite better than if
the inorganic compound was formed in the form of separated
nanoparticles due to the high contact area in the present case. On
the other hand, nitrogen doping leads to enhance p bonding
[53,54], and the basic property [55] due to the strong electron
donor behavior of nitrogen which can be the reason behind
obtaining the good specific capacitance of N-doped rGO. Moreover,
it was reported that nitrogen doping strongly enhances the specific
capacitance of rGO synthesized by microwave-based method [56].
Besides the accumulative specific capacitances in CaCO3/N-doped
rGO composite, nitrogen-doped carbon nanostructure owns high
surface nucleation sites which allows the anchorage and high
dispersion of the attached CaCO3 that results in high interaction
betweennitrogen-doped carbonaceous support and the attached
layer [57–59] which was overall leads to enhance the specific
capacitance.In order to explain the influence of electrolyte to the
inner resistance of the electrode, electrochemical impedance
spectroscopy (EIS) analysis was carried out; the results are shown
as Nyquist plots in Fig. 6(b). The Nyquist plots consist of a
semicircle in high frequency zone only for the electrode with N-
rGO/CaCO3 composite, and a quite straight line in low frequency
zone. The semicircle in the high frequency zone reflects the sum of
high charge transfer resistance (Rct), electrolyte resistance (Rs)
and contact resistance (Rc) while the straight line in low frequency
zone exhibits improved capacitive performance and low diffusion
resistance of ion [60]; moreover, the semicircle is invisible for
other electrodes, clearly showed high electron transfer resistance
due to the poor electrical conductivity. It is noteworthy mentioning
that, the left part in the Nyquist plot (i.e. at low ZRe values) is
related to formation of the electric double layer. At this region, Rct
and Cdl (capacitance of the double layer) are predominant so if the
material exhibits good electrical double layer (EDL) formation, HF
(high frequency) loop appears in this region of Nyquist plot. On the
other hand, at low frequency, the mass transport impedance is
predominant, leading to having high slop in the Nyquist plot. Such
diffusion impedance can be observed on the semi-infinite
condition, that is, when the diffusion layer thickness is continu-
ously increasing from the electrode to the bulk of the electrolyte
(but the diffusion layer is very small compared to the electrode
dimension). The aforementioned hypothesis can be exploited for
explanation of the obtained high slop in case of the pristine CaCO3
NPs with very low corresponding specific capacitance. In more
details, in case of CaCO3 NPs, almost no EDL is formed instead the
thickness of the diffusion layer increases which leads to have high
slop. With the same fashion, rGO exhibits high slop with low
corresponding specific capacitance as shown in Fig. 6A. However,
in case of N-rGo sample, the HF loop is relatively high which results
in obtaining high specific capacitance.
To further examine the specific capacitances of CaCO3,-rGO,
rGO/CaCO3, N-rGO and N-rGO/CaCO3, respectively, galvanostatic
charge/discharge tests were performed using three electrode
systems at the current density of 1 Ag
1, the results are shown in
Fig. 7(a&b). The specific capacitance from the charge/discharge
curve can be calculated based on following equation.
ðIDtÞ
C sp ¼ ð3Þ
ðmDVÞ
Were, Csp (F/g) is the specific capacitance, I (A) represents discharge
current, and m (g), DV (V) and Dt (s) designate the mass of active
 Z.K. Ghouri et al. / Electrochimica Acta 184 (2015) 193–202
Fig. 7. (a) Galvanic charge-discharge curves of CaCO3,rGO, rGO/CaCO3, N-rGO and
N-rGO/CaCO3 electrode, (b) large scale for the marked area.
material, the voltage drop upon discharge and the total discharge
time, respectively. It is noted that the charge-discharge time cycle
becomes shorter for pristine CaCO3 and rGO (Fig. 7(b)) accredited
to small specific surface area. In contrast, the charge-discharge
cycle time of rGO/CaCO3, N-rGO (Fig. 7(a)) was significantly higher
than that of CaCO3 and rGO. It can be clearly seen that the N-rGO/
CaCO3 electrode (Fig. 7(a)) presented the largest capacitance in
agreement with CV results (Fig. 5(e)). The specific capacitance
evaluated from the charge-discharge curve of CaCO3, -rGO, rGO/
CaCO3, N-rGO and N-rGO/CaCO3 electrode were found to be 0.12,
4.3, 82, 97 and 188 Fg
1,respectively. Moreover, the charge
/discharge curve of N-rGO/CaCO3 nanocomposite have an isosceles
triangle shape and a linear relationship between potential and
time, reflecting symmetrical charging-discharging mechanism.The
cyclic stability of the N-rGO/CaCO3 electrode up to 10,000 charge-
discharge cycles was also evaluated. Fig. 8 shows the specific
capacitance retention (%), while inset displays the specific
capacitance as a function of cycle number. There was minor
distortion between 3000 to 5000 cycles, followed by relative
stability in subsequent cycles and the specific capacitance of
N-rGO/CaCO3 electrode only loses 11.3 % after 10,000 charge-
discharge cycles, indicating excellent electrochemical stability.
201
Fig. 8. Speific capicistance retention as a function of cycle number.
The above results indicate that N-rGO/CaCO3 electrode could be
potentially employed as new super capacitor material.
4. Conclusion
In summary, a novel composite consisted of N-rGO/CaCO3 can
be synthesized by a facile heat reflux method. N-rGO/CaCO3
exhibits a large specific capacitance of 214 Fg
1 in 1 M KOH
electrolyte at a scan rate of 5 mV s
1 and capacitive retention
shows remarkable stability as high as 88.7% after 10,000 cycles.
Moreover, current study reveal that CaCO3 appear to be even more
suited for supercapacitor applications. Overall, the introduced
study opens new avenue for cheap and effective alkaline earth
metal family-based nanomaterials as non-precious catalyst for
super capacitors application.
Acknowledgments
This Research was financially supported by National Research
Foundation of Korea (NRF) Grant funded by the Korean Govern-
ment (MSIP) (No. 2014R1A4A1008140) and National Research
Foundation of Korea (NRF) grant funded by the Korea Government
(MSET) (No. 2012R1A2A2A01046086).
References
[1] Z.K. Ghouri, N.A.M. Barakat, M. Obaid, J.H. Lee, H.Y. Kim, Ceramics International
41 (2015) 2271–2278.
[2] Z.K. Ghouri, N.A.M. Barakat, M. Park, B.-S. Kim, H.Y. Kim, Ceramics
International 41 (2015) 6575–6582.
[3] Z.K. Ghouri, N.A. Barakat, H.Y. Kim, Energy and Environment Focus 4 (2015)
34–39.
[4] M.-y. Zhang, X.-j. Jin, Q. Zhao, New Carbon Materials 29 (2014) 89–95.
[5] D. Chen, L. Tang, J. Li, Chemical Society Reviews 39 (2010) 3157–3180.
[6] S.P.D. Meryl Stoller, Yanwu Zhu, Jinho An, S. Rodney Ruoff, NanoLetters 8 (10)
(2008) 3498–3502.
[7] Z.K. Ghouri, N.A. Barakat, A.-M. Alam, M. Park, T.H. Han, H.Y. Kim, Int. J.
Electrochem. Sci. 10 (2015) 2064–2071.
[8] S.J. Zhu, J. Zhang, J.J. Ma, Y.X. Zhang, K.X. Yao, Journal of Power Sources 278
(2015) 555–561.
[9] P. Liu, Z. Hu, Y. Liu, M. Yao, Q. Zhang, Journal of Alloys and Compounds 622
(2015) 805–811.
[10] Z.K. Ghouri, M.S. Akhtar, A. Zahoor, N.A. Barakat, W. Han, M. Park, B. Pant, P.S.
Saud, C.H. Lee, H.Y. Kim, Journal of Alloys and Compounds 642 (2015) 210–215.
[11] J. Keskinen, S. Tuurala, M. Sjödin, K. Kiri, L. Nyholm, T. Flyktman, M. Strømme,
M. Smolander, Synthetic Metals 203 (2015) 192–199.
[12] L. Timperman, A. Vigeant, M. Anouti, Electrochimica Acta 155 (2015) 164–173.
[13] A. Burke, Electrochimica Acta 53 (2007) 1083–1091.
[14] A.G. Pandolfo, A.F. Hollenkamp, Journal of Power Sources 157 (2006) 11–27.
202 Z.K. Ghouri et al. / Electrochimica Acta 184 (2015) 193–202

[15] R. Kötz, M. Carlen, Electrochimica Acta 45 (2000) 2483–2498. [39] W.S. Hummers Jr., R.E. Offeman, JACS 80 (1958) 1339.
[16] M. Mastragostino, F. Soavi, Journal of Power Sources 174 (2007) 89–93. [40] A.B. Bourlinos, D. Gournis, D. Petridis, T. Szabó, A. Szeri, I. Dékány, Langmuir 19
[17] G.A. Snook, P. Kao, A.S. Best, Journal of Power Sources 196 (2011) 1–12. (2003) 6050–6055.
[18] Z. Li, Y. Mi, X. Liu, S. Liu, S. Yang, J. Wang, Journal of Materials Chemistry 21 [41] J.W. Jang, C.E. Lee, S.C. Lyu, T.J. Lee, C.J. Lee, Applied Physics Letters 84 (2004)
(2011) 14706–14711. 2877–2879.
[19] J. Yan, Z. Fan, T. Wei, W. Qian, M. Zhang, F. Wei, Carbon 48 (2010) 3825–3833. [42] A.L. Reddy, A. Srivastava, S.R. Gowda, H. Gullapalli, M. Dubey, P.M. Ajayan, ACS
[20] R.C. Ropp, Encyclopedia of the Alkaline Earth Compounds, Elsevier, 2013. Nano 4 (2010) 6337–6342.
[21] E.T. Stepkowska, J. Perez-Rodriguez, M. Sayagues, J. Martinez-Blanes, Journal of [43] X. Li, H. Wang, J.T. Robinson, H. Sanchez, G. Diankov, H. Dai, J Am Chem Soc 131
thermal analysis and calorimetry 73 (2003) 247–269. (2009) 15939–15944.
[22] K.H. An, W.S. Kim, Y.S. Park, Y.C. Choi, S.M. Lee, D.C. Chung, D.J. Bae, S.C. Lim, Y. [44] C.P. Ewels, M. Glerup, Journal of nanoscience and nanotechnology 5 (2005)
H. Lee, Advanced Materials 13 (2001) 497–500. 1345–1363.
[23] D.A. Areshkin, C.T. White, Nano Letters 7 (2007) 3253–3259. [45] Y. Shao, S. Zhang, M.H. Engelhard, G. Li, G. Shao, Y. Wang, J. Liu, I.A. Aksay, Y. Lin,
[24] S. Vivekchand, C.S. Rout, K. Subrahmanyam, A. Govindaraj, C. Rao, Journal of Journal of Materials Chemistry 20 (2010) 7491–7496.
Chemical Sciences 120 (2008) 9–13. [46] Z.H. Sheng, L. Shao, J.J. Chen, W.J. Bao, F.B. Wang, X.H. Xia, ACS Nano 5 (2011)
[25] L. Wang, D. Wang, Z. Dong, F. Zhang, J. Jin, Nano Letters 13 (2013) 1711–1716. 4350–4358.
[26] C. Berger, Z. Song, X. Li, X. Wu, N. Brown, C. Naud, D. Mayou, T. Li, J. Hass, A.N. [47] T. Horikawa, N. Sakao, T. Sekida, J.i. Hayashi, D.D. Do, M. Katoh, Carbon 50
Marchenkov, Science 312 (2006) 1191–1196. (2012) 1833–1842.
[27] K.S. Novoselov, A.K. Geim, S. Morozov, D. Jiang, Y. Zhang, S. Dubonos, I. [48] C. Pevida, T.C. Drage, C.E. Snape, Carbon 46 (2008) 1464–1474.
Grigorieva, A. Firsov, Science 306 (2004) 666–669. [49] V. Datsyuk, M. Kalyva, K. Papagelis, J. Parthenios, D. Tasis, A. Siokou, I. Kallitsis,
[28] A.K. Geim, K.S. Novoselov, Nature materials 6 (2007) 183–191. C. Galiotis, Carbon 46 (2008) 833–840.
[29] J. Bai, X. Zhong, S. Jiang, Y. Huang, X. Duan, Nature nanotechnology 5 (2010) [50] T.I.T. Okpalugo, P. Papakonstantinou, H. Murphy, J. McLaughlin, N.M.D. Brown,
190–194. Carbon 43 (2005) 153–161.
[30] Z. Chen, Y.-M. Lin, M.J. Rooks, P. Avouris, Physica E: Low-dimensional Systems [51] N.A.M. Barakat, A.G. El-Deen, G. Shin, M. Park, H.Y. Kim, Materials Letters 99
and Nanostructures 40 (2007) 228–232. (2013) 168–171.
[31] D. Deng, X. Pan, L. Yu, Y. Cui, Y. Jiang, J. Qi, W.-X. Li, Q. Fu, X. Ma, Q. Xue, G. Sun, X. [52] T. Kuila, A.K. Mishra, P. Khanra, N.H. Kim, M.E. Uddin, J.H. Lee, Langmuir 28
Bao, Chemistry of Materials 23 (2011) 1188–1193. (2012) 9825–9833.
[32] Z. Lin, M. -k. Song, Y. Ding, Y. Liu, M. Liu, C. -p. Wong, Physical Chemistry [53] Y. Shao, G. Yin, Y. Gao, P. Shi, J Electrochem. Soc. 153 (2006) A1093–A1097.
Chemical Physics 14 (2012) 3381–3387. [54] S. Maldonado, K.J. Stevenson, J. Phys. Chem. B 109 (2005) 4707–4716.
[33] X. Li, H. Wang, J.T. Robinson, H. Sanchez, G. Diankov, H. Dai, Journal of the [55] S. Dommele, K.P. áde Jong, Chemical Communications (2006) 4859–4861.
American Chemical Society 131 (2009) 15939–15944. [56] K. Gopalakrishnan, A. Govindaraj, C. Rao, Journal of Materials Chemistry A 1
[34] H.M. Jeong, J.W. Lee, W.H. Shin, Y.J. Choi, H.J. Shin, J.K. Kang, J.W. Choi, Nano (2013) 7563–7565.
letters 11 (2011) 2472–2477. [57] X. Xu, Y. Zhou, T. Yuan, Y. Li, Electrochim Acta 112 (2013) 587–595.
[35] Y. Zhang, K. Fugane, T. Mori, L. Niu, J. Ye, Journal of Materials Chemistry 22 [58] B. Vinayan, K. Sethupathi, S. Ramaprabhu, Int. J. Hydrogen Energy 38 (2013)
(2012) 6575–6580. 2240–2250.
[36] A.L.M. Reddy, A. Srivastava, S.R. Gowda, H. Gullapalli, M. Dubey, P.M. Ajayan, [59] Y. Xin, J.-g. Liu, X. Jie, W. Liu, F. Liu, Y. Yin, J. Gu, Z. Zou, Electrochim. Acta 60
Acs Nano 4 (2010) 6337–6342. (2012) 354–358.
[37] W.S. Hummers Jr., R.E. Offeman, Journal of the American Chemical Society 80 [60] T. Kuila, P. Khanra, N.H. Kim, J.K. Lim, J.H. Lee, Journal of Materials Chemistry A
(1958) 1339. 1 (2013) 9294–9302.
[38] C.F. Chang, Q.D. Truong, J.R. Chen, Applied Surface Science 264 (2013) 329–334.