Journal of Alloys and Compounds: D.A.L. Almeida, A.B. Couto, N.G. Ferreira
Journal of Alloys and Compounds: D.A.L. Almeida, A.B. Couto, N.G. Ferreira
a r t i c l e i n f o a b s t r a c t
Article history: Electrochemical supercapacitor (EC) is a kind of device able to generate and store clean energy, which
Received 1 October 2018 makes it the object of intense research. This work proposes a double layer capacitance combination of
Received in revised form electrochemical reduced graphene oxide (rGO) and carbon fiber (CF) in addition to pseudocapacitive
14 February 2019
behavior of polyaniline (PAni) to produce PAni/rGO/CF ternary composite with high capacitive response.
Accepted 16 February 2019
Available online 19 February 2019
rGO/CF and PAni/rGO/CF are obtained by electrochemical methodology. The morphological and structural
analyses by scanning electron microscopy, X-ray diffraction, and Raman spectroscopy show that these
nanostructured composite materials can be produced successfully. rGO/CF and PAni/rGO/CF samples are
Keywords:
Polyaniline
evaluated electrochemically by cyclic voltammetry (CV), electrochemical impedance spectroscopy, and
Graphene oxide charge/discharge tests. PAni/rGO/CF ternary composite presents a better performance in terms of specific
Carbon fiber capacitance and electrochemical reversibility than that of rGO/CF composite and CF electrodes. The re-
Composite characterization sults show that this ternary composite can be a promising electrode for applications in supercapacitors.
Supercapacitor © 2019 Elsevier B.V. All rights reserved.
https://doi.org/10.1016/j.jallcom.2019.02.194
0925-8388/© 2019 Elsevier B.V. All rights reserved.
454 D.A.L. Almeida et al. / Journal of Alloys and Compounds 788 (2019) 453e460
graphene oxide (rGO) may be an ideal support material for PAni, distilled aniline. The obtained PAni/rGO/CF ternary composite was
because its interconnected network can act as a template matrix, washed in acid solution and vacuum dried. The morphological and
whose structures are covered by PAni thin films, giving rise to a structural analyses were investigated by field emission gun-
nanostructured composite with high surface area, which can scanning electron microscopy (FEG-SEM) from a TESCAN MIRA 3
simultaneously improve its faradaic capacitance and mechanical microscope system, by Raman spectra recorded using a Horiba
stability. Thin layers of PAni on rGO can indeed reduce the path of Scientific LabRAM HR Evolution microscope system with 514 nm
diffusion and migration of the electrolyte ions during the fast laser beam line, and by X-ray diffraction from a Phylips X'pert
charge/discharge processes, besides increasing the electrode elec- system, respectively. The electrochemical analyses in
trochemical activity [9]. 1.0 mol L1 H2SO4 solution are recorded in a three electrode system
In this context, carbon fiber (CF) also offers the advantage to be using Ag/AgCl electrode as reference electrode and a platinum
used as electrodes for rGO deposition because its 3D structure, sheet as counter-electrode in deaired solution with N2 using a
which decreases the packing of the graphene sheets, avoiding the potentiostat PGSTAT 302 with FRA module (AUTO-
binders normally used to prepare the binary composite rGO/CF not LABeEcoChemie). The charge/discharge (CD) tests in
to mention its high surface area. Despite CF felt low capacitance 1.0 mol L1 H2SO4 solution are obtained by applying constant cur-
value, it is composed of conductive micro fibers susceptible of being rent of ±1.0, 0.75 and 0.5 mA (Ecut-off from 0.1e0.78 V vs. Ag/AgCl).
wrapped by graphene sheets for subsequent coating with polymer Cyclic voltammograms (CV) are recorded in previously defined
films. For PAni/rGO/CF, the resulting architecture of this association potential range at scan rate from 5 to 400 mV s1. The electro-
can act together to improve electrical contact between rGO and chemical impedance spectroscopy (EIS) measurements are per-
PANI, since the sheets of GO coated the CF fibers, which are seemed formed at open circuit potential (OCP) with ±10 mV of the potential
as three-dimensional intertwined conductive wires, resulting in a amplitude in the frequency range from 103e105 Hz in
binary 3D rGO/CF that were also coated by PAni films. CF inter- 1.0 mol L1 H2SO4.
connected three-dimensional structure acts as a templated
framework directly interfering in the pore structures formed in the 3. Results and discussions
composite material, because PAni films did not grow only on the
outer surface, but also inside the binary composite acting as a link 3.1. Morphological and structural analyses
among the adjacent structures of rGO/CF creating a porous 3D
network. Thus, the PAni is not only responsible for the best elec- Fig. 1 presents the rGO/CF binary and the PAni/rGO/CF ternary
trical contact among the materials, but also resulting in a greater composite morphologies. As shown in FEG-SEM images (Fig. 1(a
specific surface area, increasing the electrode/electrolyte contact and b)), the CF is totally covered by rGO sheets. In higher magni-
playing an important role in the specific capacitance of ternary fication (Fig. 1 (c)) it is observed that rGO consists of wrinkled and
electrode as well as in its cyclic stability. Consequently, these con- aggregated sheets like a silk veil on CF substrate. These crumpled
tributions make a significant difference to the charge storage of and overlaid sheets are characteristic of rGO indicating the success
supercapacitors devices. Accordingly, the production and charac- of this electrochemical process on CF substrate. After PAni elec-
terization of binary rGO/CF and ternary PAni/rGO/CF composites are trochemical deposition (Fig. 1(def)), it is noted that no visible long
discussed in detail. We show the electrochemical measurements of fiber or big granular particles of PAni are formed on the rGO/CF
cyclic voltammetry (CV), electrochemical impedance spectroscopy, composite. It is clearly seen that a thin and homogenous PAni layers
and charge/discharge tests for both composites. For this purpose, grow on rGO sheets. It is noteworthy that the PAni/rGO/CF surface is
the combination of both double layer capacitance from rGO/CF and rougher than that of rGO/CF composite. This fine and rougher PAni
pseudocapacitive behavior of PAni is used to product the PAni/rGO/ texture covering the whole rGO/CF composite may improve its
CF ternary composite with high capacitive response, aiming the active area making this ternary composite suitable to keep the
electrode performances in supercapacitors. properties of these constituent materials to be applied as electrode
in supercapacitor.
2. Experimental Aiming to evaluate the structural changes of natural graphite,
GO, and rGO, X-ray diffraction (XRD) analyses are used. Fig. 2 dis-
CF samples were produced from polyacrylonitrile (PAN) pre- plays XRD patterns for the raw graphite powder, GO obtained from
cursor at heat treatment temperature of 1000 C and were cut in the oxidation and exfoliation processes of graphite by modified
size of 1 cm2 with thickness 2 mm, and density of 0.094 g cm3 and Hummer's method, and rGO electrodeposited on CF substrate.
using as porous subtract for rGO deposition. GO is obtained by Natural graphite displayed a strong characteristic (002) peak at
modified Hummer's method [14] from reagent graphite powder 26.5 . After its oxidation and exfoliation processes, the GO (002)
(Synth 98%). Next, 180 mg GO powder was dissolved in 30 mL peak is observed at 10.1, which is due to the formation of oxygen-
distilled water and this solution was previously sonicated before containing functional groups associated to the complete oxidation
deposition (Sonic Vibra Cell VC750) with pulse of 15 s and 25% of graphite to graphene oxide. The successful electroreduction of
amplitude, for 30 min in order to exfoliation of GO to GO sheets. GO into rGO on the CF substrate is evidenced by the disappearance
After the GO solution was centrifuged (KASVI modelo K14-4000) at of the characteristic GO diffraction peak while a broad (002) peak
4000 rpm for 15 min to remove the residual particulate materials, showed up at around 2q ¼ 25.4 caused by the removal of some
obtaining a homogeneous GO dispersion. For production rGO/CF oxygen-containing functional groups in agreement with the typical
binary composite electrode, the CF (work electrode) was immersed characteristic peak reported in the literature [16]. Thus, the rGO/CF
in 25 mL of the GO solution (3 mg mL1) containing 0.1 mol L1 composite presented the XRD pattern similar to pure CF substrate,
LiClO4. The GO was electrodeposited and reduced simultaneously whose analyzes have already been widely discussed in previous
on CF under potentiostatic mode, at a fixed potential of 1.25 V vs. works [17].
Ag/AgCl/KCl(sat) for 15 min in, similar to the methodology adopted Furthermore, Raman spectroscopy is a traditionally and widely
by Cao et al. [15], resulting in the rGO/CF binary composite. After- used technique to detect small changes in the structural properties
wards, the PAni was electrodeposited on rGO/CF binary composite of the graphene-based materials. Nevertheless, the characteriza-
under galvanostatic mode with current density of 5 mA cm2 for tion of GO and rGO through this technique is still an object of
10 min in 0.5 mol L1 H2SO4 aqueous solution with 0.1 mol L1 discussion in the literature [18e21]. Fig. 3 presents the Raman
D.A.L. Almeida et al. / Journal of Alloys and Compounds 788 (2019) 453e460 455
Fig. 3. Raman spectra for CF, GO, rGO/CF, and PAni/rGO/CF using the incident radiation
Fig. 2. XRD patterns of natural graphite, CF, GO, and rGO/CF samples.
of 514.5 nm.
spectra for CF, GO, rGO/CF, and PAni/rGO/CF. structure, some authors use the ID/IG ratio of intensities of bands as
The CF, GO, and rGO spectra depicted three representative a structural organization parameter [23e25], and it has been
peaks, namely as D band (at around 1350 cm1) related to the related to the inverse of the crystallite size (La) through the
disorder in the graphite lattice, and G band (at around 1590 cm1) Tuinstra-Koenig model [26]. The ID/IG values and crystallite sizes
in neat graphite, related to the sp2 carbon networks presence. The (La) are calculated from Tuinstra-Koenig equation of GO and rGO/CF
bands centered at around 2700 cm1, corresponds to the second and are listed in Table 1.
order Raman spectrum, also characteristic of crystalline graphite The ID/IG value increased from 0,97 to 1.17, highlighting the
[22]. Overall, due to the presence of defects/border in the graphene presence of more defects, as a consequence of the lowest average
456 D.A.L. Almeida et al. / Journal of Alloys and Compounds 788 (2019) 453e460
(b)
Fig. 4. Multiple peak-fit of 2D region Raman spectra for (a) GO and (b) rGO samples.
D.A.L. Almeida et al. / Journal of Alloys and Compounds 788 (2019) 453e460 457
Fig. 5. (a) CV curves of CF, rGO/CF, and PAni/rGO/CF at 25 mV s1 in H2SO4 mol L1 solution; (b) Voltammograms of PAni/rGO/CF at a scan rate from 5 mV s1 to 400 mV s1.
The galvanostatic charge/discharge curves of CF, rGO/CF and exhibit a symmetrical triangular line typical of a double-layer
PAni/rGO/CF are shown in Fig. 6 (a). The measurements are carried capacitor. The curves of PAni/rGO/CF presented two distinct
out in the voltage range from 0 to 0.78 V at a current density of levels. The region (1), showed a shoulder related to faradic process
1 mA cm1. The rGO/CF showed linear charge/discharge profile (PAni pseudocapacitive performance) while the region (2) is linear
indicating a capacitive behavior mainly due to electric double layer and represented the capacitive process [37].
formation. The curves of the PAni/rGO/CF ternary composite The EIS measurements are used to evaluate the resistance and
showed a long time of the charge/discharge, improving their capacitive characters of the electrodes. Fig. 7(a and b) shows the
capacitance values, attributed to the high electrode surface area Nyquist diagrams for CF, rGO, and PAni/rGO/CF. At low frequency
and the PAni pseudocapacitive behavior. In addition, according to region (Fig. 7 (a)) a vertical line parallel to Z00 axis is observed for
the literature, one of the important parameters to be considered for PAni/rGO/CF, which indicated an ideal capacitive behavior, while
an ideal capacitor of the high power density is low internal resis- for CF and rGO/CF these lines are more inclined, indicating that
tance (IR). The measurement of the internal resistance of the cell these electrodes did not present pure capacitive behaviors [9]. The
can be done through the IR drop in the charge-discharge curve, ohmic resistance values of the electrolyte (RS) are obtained by the
where the current reversed its polarity [34]. The rGO/CF binary first extrapolation of the real axis (Z0 ), at high frequencies, in Fig. 7
composite presented the highest IR drop value while the PAni/rGO/ (b), whose values are at around 1.0 U for CF and rGO/CF while for
CF electrode showed the lowest IR drop value. The decrease of IR PAni/rGO/CF the resistance is at around 0.70 U. Usually the Nyquist
drop indicated that there is an increase in the electrical conduc- diagrams show a semicircle, which is simulated by a parallel
tivity [35], probably due to efficient electrolyte diffusion inside the combination of the interfacial capacitance and the charge transfer
electrode and low charge transfer resistance [36]. The PAni incor- resistance (RCT) in the region of medium frequencies. The RCT values
poration, which forms an interconnected network as shown in of the electrodes are found in the second extrapolation of the Z0 , in
Fig. 1(e and f), can be acting as inner current collector increasing the the end of the semicircles. The values obtained are 3.2, 5.3, and 1 U
conductivity of this electrode, besides supplying a larger area of for CF, rGO/CF, and PAni/rGO/CF, respectively. The decrease of the
active surface, accessible to the electrolyte. semicircle after the incorporation of PAni content in the rGO/CF is
Fig. 6 (b) shows the CD curves of the composite electrode PAni/ notable. The ternary composite showed the lowest RCT value and
rGO/CF at different current densities, in order to understand the more capacitive behavior compared to those of CF and rGO/CF,
behavior of this electrode. The lines of the curves are not straight, demonstrating that the ternary composite has a faster ion diffusion
similar to those observed in those of other carbon structures such and charge transfer due to its high surface area. This result can be
as carbon nanotubes, carbon blacks, and activated carbon, which related to the fact that the working electrode is highly porous,
Fig. 6. (a) CD curves of CF, rGO/CF, and PAni/rGO/CF at a current density of 0.5 A cm1 in H2SO4 1.0 mol L1; (b) CD curves of PAni/rGO/CF obtained at three current densities: 0.50,
0.75, and 1 mA cm1 in H2SO4 1.0 mol L1.
458 D.A.L. Almeida et al. / Journal of Alloys and Compounds 788 (2019) 453e460
Fig. 7. (a) Nyquist plot of all frequencies range studied for samples CF, rGO/CF and PAni/rGO/CF in 1.0 mol L1 H2SO4. (b) Zoom view of the previous plot in region of medium and
high frequencies. (ced) Bode plots at frequency range from 105 to 103 Hz.
which facilitates the access of the electrolyte ions, contributing to a is the angular frequency, and Z(u) is the impedance. Based on this
fast and reversible reaction decreasing the RCT, besides the synergic relationship, the components of complex capacitance can be
effect resulting from the association of PAni with rGO as discussed calculated by the following expressions:
above.
Fig. 7 (c,d) also shows the Bode plots, where the impedance CðuÞ ¼ Z
ðuÞ=ujZðuÞj2 (2)
modulus vs. frequency plot are presented in Fig. 7 (c). The total
resistance values, referring to the sum of RS, RCT, and the ohmic
resistance (R) of the electrodes at low frequencies [38], are 352, CðuÞ ¼ ZðuÞ=ujZðuÞj2 (3)
3243, and 10315 U for PAni/rGO/CF, rGO/CF, and CF, respectively.
In the expressions (2) and (3), C'(u) is the real part of the
PAni/rGO/CF showed the lowest total resistance value compared to
complex capacitance, Z' (u) is the real impedance, and Z'' (u) is the
those of rGO/CF and CF, besides presenting the maximum phase
imaginary impedance. According to the literature, the capacitance
angle at around 84 Fig. 7 (d), i. e., near to 90 , similar to a pure
of the cell measured during discharge at constant current corre-
capacitor profile [39], whereas, these values are 77 and 76 for rGO/
sponds to the C' (u) values in low frequency region. On the other
CF and CF electrodes, respectively. These data corroborate with the
hand C''(u), which corresponds to the imaginary part of the com-
CD and CV measurements, in which the ternary composite showed
plex capacitance, can be attributed to the energy dissipation from
the best electrochemical performance and typical capacitive
irreversible process, which may result in a hysteresis [40]. The di-
behavior.
agrams of real part C' vs. frequency of CF, rGO/CF, and PAni/rGO/CF
Taberna et al. have reported another alternative to describe the
are shown in Fig. 6 (a). The values of C' for PAni/rGO/CF sample
supercapacitor behavior by using the impedance measurements to
increased markedly as the frequency decreased. Such values
transform the data to complex capacitance form, applying the
exceeded in two orders of magnitude the values of CF and one order
equation [40]:
of magnitude of rGO/CF. The literature reported that in the region of
low frequency, the maximum value of capacitance is reached, due
CðuÞ ¼ 1=iuZðuÞ (1) to the fact that the ions present in the solution have the time
necessary to permeate the pores of the electrode and to establish
where C (u) is the complex capacitance, i is an imaginary number, u the electric double layer on its surface [38]. Thus, the overall
D.A.L. Almeida et al. / Journal of Alloys and Compounds 788 (2019) 453e460 459
capacitance of double layer of electrodes at low frequency (103 Hz) lowest charge accumulation, i.e., a value of the order of 103 F. For
is obtained, whose values are 430, 36, and 10 mF, for PAni/rGO/CF, rGO/CF the t0 is 0.8 s (Fig. 8 (d)) and its charge accumulated
rGO/CF, and CF, respectively. increased by one order of magnitude compared to that of CF. The t0
Other important data that can be explored using the EIS tech- of PAni/rGO/CF is 4 s (Fig. 8 (e)), in contrast, its charge storage ca-
nique is the relaxation time constant, t0. According to literature this pacity increased two orders of magnitude when compared to that
constant represents the minimum time required so that all energy of CF electrode. Therefore, this ternary electrode proved its
is released by the supercapacitor with efficiency greater than 50% advanced applicability in high energy storage devices.
[41,42]. Wei et al. reported that for commercial devices, this mini-
mum time needed is usually in the range of 10e100 seconds. The 4. Conclusions
imaginary part C'' vs. frequency for all electrodes are presented in
Fig. 8 (b). Because the charge accumulation is much larger for PAni/ The ordered rGO/CF and PAni/rGO/CF composites were suc-
rGO/CF than those of rGO/CF and CF, its response time is also much cessfully produced trough simple and inexpensive electrochemical
higher, hindering the response times of the rGO/CF and CF elec- method. The morphological and structural analyses showed the
trodes (Fig. 8 (b)). Thus, to better visualize and evaluate C' and C'', characteristic aggregates with irregular and flakes-like shape with
the complex capacitance values vs. frequency are plotted in high particle density of rGO on CF substrate. The PAni deposits
Fig. 8(cee), for the three electrodes, where the left-hand axis cor- depicted a thin and homogenous PAni layer grown throughout the
responds to the real part of the complex capacitance and the right- rGO/CF surface, increasing its roughness. Both second-order Raman
hand axis to its imaginary part, in separate way for each sample. It is results and first-order Raman spectra showed more structural de-
verified in Fig. 8 (c) that CF electrode presented the shortest fects for rGO than those for GO sample. Concerning the ternary
response time (0.04 s). On the other hand, it also presented the composite, the PAni/rGO/CF Raman spectrum showed the
Fig. 8. Plots of (a) C0 and (b) C00 vs. frequency of the CF, rGO/CF, and PAni/rGO/CF at frequency range from 105 to 103 Hz. Representation of complex capacitance vs. frequency, where
C' is represented on the left-hand axis and C' the right-hand axis in medium and high frequency regions: (c) CF, (d) rGO/CF, and (c) PAni/rGO/CF electrodes.
460 D.A.L. Almeida et al. / Journal of Alloys and Compounds 788 (2019) 453e460
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