Brza - 2020 - Arabian Journal

Arabian Journal of Chemistry (2020) xxx, xxx–xxx
King Saud University
Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com
ORIGINAL ARTICLE
Metal framework as a novel approach for the

fabrication of electric double layer capacitor device
with high energy density using plasticized Poly(vinyl
alcohol): Ammonium thiocyanate based polymer
electrolyte
M.A. Brza a, Shujahadeen B. Aziz b,c,*, H. Anuar a, Fathilah Ali d, M.H. Hamsan e, M.
F.Z. Kadir f, Rebar T. Abdulwahid g
a
Department of Manufacturing and Materials Engineering, Faculty of Engineering, International Islamic University of
Malaysia, Kuala Lumpur, Gombak 53100, Malaysia
b
Advanced Polymeric Materials Research Lab., Department of Physics, College of Science, University of Sulaimani, Qlyasan
Street, Sulaimani 46001, Iraq
c
Department of Civil Engineering, College of Engineering, Komar University of Science and Technology, Sulaimani, 46001,
Kurdistan Regional Government, Iraq
d
Department of Biotechnology Engineering, Faculty of Engineering, International Islamic University of Malaysia, Kuala
Lumpur, Gombak 53100, Malaysia
e
Institute for Advanced Studies, University of Malaya, 50603 Kuala Lumpur, Malaysia
f
Centre for Foundation Studies in Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
g
Department of Physics, College of Education, University of Sulaimani, Old Campus, Kurdistan Regional Government,
Sulaimani 46001, Iraq
Received 6 June 2020; accepted 9 August 2020
KEYWORDS Abstract High performance electric double-layer capacitors (EDLCs) based on poly (vinyl alco-
PVA polymer electrolyte; hol) (PVA): ammonium thiocyanate (NH4SCN):Cu(II)-complex plasticized with glycerol (GLY)
Glycerol plasticizer; have been fabricated. The maximum DC ionic conductivity (rDC) of 2.25 10-3 S cm1 is achieved
Cu(II)-complex; at ambient temperature. The X-ray diffraction (XRD) patterns confirmed that the addition of both
Electrochemical and EDLC Cu(II)–complex and GLY enhanced the amorphous region within the samples. Through the Four-
* Corresponding author at: Advanced Polymeric Materials Research Lab., Department of Physics, College of Science, University of Sulaimani,
Qlyasan Street, Sulaimani 46001, Iraq.
E-mail address: [email protected] (S.B. Aziz).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
https://doi.org/10.1016/j.arabjc.2020.08.006
1878-5352 Ó 2020 The Author(s). Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Brza, M.A. et al., Metal framework as a novel approach for the fabrication of electric double layer capacitor device with high energy
density using plasticized Poly(vinyl alcohol): Ammonium thiocyanate based polymer electrolyte. Arabian Journal of Chemistry (2020), https://doi.org/10.1016/j.
arabjc.2020.08.006
2 M.A. Brza et al.
ier transform infrared (FTIR) the interactions between the host polymer and other components of
the prepared electrolyte are observed. The FESEM images reveal that the surface morphology of
the samples showed a uniform smooth surface at high GLY concentration. This is in good agree-
ment with the XRD and FTIR results. Transference numbers of ion (tion) and electron (tel) for the
highest conducting composite polymer electrolyte (CPE) are recognized to be 0.971 and 0.029,
respectively. The linear sweep voltammetry (LSV) revealed that the electrochemical stability win-
dow for the CPE is 2.15 V. These high values of tion and potential stability established the suitability
of the synthesized systems for EDLC application. Cyclic voltammetry (CV) offered nearly rectan-
gular shape with the lack of Faradaic peak. The specific capacitance and energy density of the
EDLC are nearly constant within 1000 cycles at a current density of 0.5 mA/cm2 with average of
155.322F/g and 17.473 Wh/Kg, respectively. The energy density of the EDLC in the current work
is in the range of battery specific energy. The EDLC performance was found to be stable over 1000
cycles. The low value of equivalent series resistance reveals that the EDLC has good electrolyte-
electrode contact. The EDLC exhibited the initial high power density of 4.960 103 W/Kg.
Ó 2020 The Author(s). Published by Elsevier B.V. on behalf of King Saud University. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction An electrolyte film and two porous electrodes are included

in the EDLC device. Mostly carbon-based electrodes are used
Supercapacitors (SCs) can be categorized into three kinds of for creating these SCs (Jayalakshmi and Balasubramanian,
electrochemical capacitor (EC) which are known as electric 2008). The different carbon-based electrode materials used in
double-layer capacitor (EDLC), pseudocapacitor, and hybrid EDLCs are carbon aerogels, activated carbon (AC), carbon
SCs. In the EDLC the electric energy is stored based on elec- nanotubes, carbon nanosize, graphites, and carbon nanofibers
trosorption process (charge–discharge) when the Helmholtz (Zhang et al., 2009). AC is used in this study as an electrode
double layers are formed on porous electrodes through move- because of its high conductivity, chemical stability, large sur-
ment of ions inside the electrolyte (Lim et al., 2014). Pseudoca- face area (>1000 m2g1), cost effective, and high porosity
pacitor stores energy faradaically by chemical interaction (>2 nm pore width) (Syahidah and Majid, 2013; Zhao et al.,
between the electrolyte and electrode for example redox reac- 2018). At the same time, the electrolyte can be liquid elec-
tion. The process of charge storage used in hybrid capacitors trolyte (LE), solid polymer electrolyte (SPE), gel polymer elec-
is a mix of the both faradaic reaction and non-faradaic reac- trolyte (GPE) (Asnawi et al., 2020). The SPE outweigh LE in
tion. EDLC is the typical non-faradaic SC. The charge–dis- many substantial characteristics such as electrolyte leakage,
charge cycles just involve ions adsorption on the surface of better safety, high flexibility, light weight, and excellent ther-
the electrodes. It is promising to attain high energy density mal stability (Lim et al., 2014; Shen et al., 2017). These features
(Ed) and power density (Pd) using EDLC. (Mohd Abdah can essentially enhance the EDLC electrochemical perfor-
et al., 2020; Hadjipaschalis et al., 2009; Winter and Brodd, mances. Additionally, the increased demand for flexible elec-
2004). ECs are devices which can occupy the spaces between tronic devices resulted in an increasing trend of employing
battery and electrostatic capacitor with regard to Ed and Pd polymer hydrogels as the separators and electrolytes for flexi-
as shown in Ragone plot (see Fig. 1). The Ragone plot is a ble electrochemical energy storage devices (Wang et al., 2018).
chart employed for comparing the performance of several Compared to SPE, hydrogel electrolyte consists of elastic
energy storage devices for example SCs, fuel cells, conven- crosslinked hydrated polymer chains that trap water in the
tional capacitors, and batteries (Jayalakshmi and interstitial spaces of the polymer matrices mainly by surface
Balasubramanian, 2008). The achieved Ed in the current work tension (Gong, 2014). This makes the hydrogel electrolyte
is 17.473 Wh/Kg throughout 1000 cycles which is in the range appear usually wet, which gives a tough and soft property to
of Ed of batteries (see Fig. 1). the electrolyte (Gong, 2014).
In recent decades, biodegradable polymers have been
widely studied to be employed in the renewable energy sources
and electrochemical energy storage devices to solve the envi-
ronmental issues (Saidi et al., 2019). However, the electrical
and mechanical properties of these polymers need enhance-
ment in order to be used in the energy devices (Saidi et al.,
2019). Various host polymers have been widely investigated
in this field, such as chitosan (Aziz et al., 2020), hydroxylethyl
cellulose (HEC) (Chong et al., 2018), Polyethylene oxide
(PEO) (Hadi et al., 2020), poly(vinyl alcohol) (PVA) (Farah
et al., 2019), methylcellulose (MC) (Aziz et al., 2020), N, N-
dimethyl acrylamide (DMA) (Bashir et al., 2020), and
polyacrylamide-co-acrylic acid (PAAC) (Saminatha
Kumaran et al., 2018). Previous studies are shown that both
Fig. 1 Ragone plot of Ed versus Pd for numerous electrochemi- mechanical and electrical properties of PVA can be consider-
cal energy storage devices (Winter and Brodd, 2004). able enhanced when doped with glycerol (GLY) and different
arabjc.2020.08.006
Metal framework as a novel approach for the fabrication of electric double layer capacitor 3
salts such as calcium chloride (CaCl2) and sodium chloride ol) and GLY (molecular weight = 92.09382 g/mol). HmbG
(NaCl) (Jiang et al., 2015; Peng et al., 2019). chemicals, EMPLURA, and Timcal provided ammonium thio-
In this research, poly (vinyl alcohol) (PVA) was preferred as cyanate (NH4SCN) (molecular weight = 76.12 g/mol), N-
a host polymer due to its biodegradable capability, low cost, Methyl-2-pyrrolidone (NMP) (molecular weight = 99.13 g/m
and easy processability. Ammonium thiocyanate (NH4SCN) ol), and carbon black (molecular weight = 12.01 g/mol),
was used in the current study as a low lattice energy salt to respectively. Magna value delivered both of the polyvinylidene
deliver H+ to the CPE system (Abd El-Kader et al., 2002). Sri- fluoride (PVdF) (average molecular weight = ~534,000 by
vastava et al. (Srivastava et al., 1995) have stated that the GPC) and activated carbon (AC) (RP20) (molecular
charge carrier in PEO combined with NH4SCN is the H+. weight = 12.01 g/mol).
NH4SCN has low lattice energy of 605 kJ.mol1 compared
to other ammonium salts, such as NH4Br (667 kJ mol1), 2.2. Electrolyte preparation
NH4Cl (694.7 kJ mol1), NH4NO3 (648.9 kJ mol1), NH4F
(834.5 kJ mol1), NH4I (626 kJ mol1), etc. (Jenkins and One gram of PVA was dissolved in 40 mL of distilled water.
Morris, 1976; Kadir, 2010). Therefore, it is possible to dissoci- The solution was stirred using magnetic stirrer at the temper-
ate it easily into cations and anions when inserted in water as a ature of 80 °C for around 60 min to prepare the PVA solution.
solvent. This means, larger number ammonium ions are The PVA solution was then left to cool down to room temper-
offered by NH4SCN to the polymer. The addition of Cu(II)– ature. Then, fixed amount of 50 wt% of NH4SCN were added
complex to the polymer electrolyte (PE) was attempted to to the PVA solutions and stirred constantly with magnetic stir-
improve the performance of the electrolyte films via establish- rer at ambient temperature until the salt was fully dissolved in
ing an amorphous nature which is crucial for ion transport the PVA polymer solutions. Later, PVA:NH4SCN was
process. In this study, glycerol (GLY) was also chosen as an included with 10 mL of Cu(II)-complex (synthesis of Cu(II)-
appropriate plasticizer since it enhances DC conductivity complex was described in our previous work in materials
(rDC) because of the existence of three groups of hydroxyl and methods section in ref. (Brza et al., 2019). Subsequently,
(OH). It is believed that the high dielectric constant value the solutions were mixed and stirred to obtain a good disper-
(er) of 42.5 for GLY can reduce the attraction force amongst sion of Cu(II)-complex in the solution. After that, the PVA:
the cations and anions of the salt, and also weaken the force NH4SCN:Cu(II)-complex were plasticized with 10, 20, 30,
between chains of the polymers (Shukur and Kadir, 2014, and 40 wt% GLY and then the prepared samples were coded
2015). as PGNC-1, PGNC-2, PGNC-3, and PGNC-4, respectively.
In our previous study it was revealed that the amorphous Finally, the plasticized solutions were stirred and mixed until
structure of PVA polymer enhanced through the inclusion of a homogeneous solution was reached and then preserved in
Cu(II)–complex (Brza et al., 2019). To the best of our knowl- the plastic Petri dishes and left for drying at room temperature.
edge, no study has been reported in literature regarding the For drying better, the fabricated CPE films were preserved in a
role of metal complex (e.g. Cu(II)-complex) or metal frame- dessicator comprising silica gel before characterisations.
work on EDLC performance. Mohamad & Arof, (Mohamad
and Arof, 2007) have fabricated the plasticized system of 2.3. Characterization techniques
PVA–KOH–Propylene carbonate (PC)–Al2O3. The results
showed that the samples conductivity could be significantly
X-Ray Diffraction (XRD) spectra were achieved through the
increased with raising the PC plasticizer content (Mohamad
use of Empyrean X-ray diffractometer, (PANalytical, Nether-
and Arof, 2007). Lim et al., (Lim et al., 2014) fabricated EDLC
land) with operating voltage of 40 103 V and operating cur-
device based on AC electrodes and PVA:LiClO4:TiO2. They
rent of 40 10-3 A. The CPE films were scanned with a CuKa
are noted that the insertion of TiO2 into the PVA–LiClO4 sys-
X-ray monochromatic radiation at 0.15406 nm wavelength
tem resulted in the rDC of 1.3 10-4 S cm1 and specific
and the 2h glancing angle was ranged from 10° to 80° with
capacitance (Cd) value of 12.5F g1. Nonetheless, the Cd of
0.1° step size.
the CPE is still low and the addition of TiO2 was not signifi-
To study the PVA film as well as CPE films, Fourier Trans-
cantly enhanced the electrochemical performances of the
form Infrared (FTIR) spectrophotometer (Thermo Scientific,
EDLC. Thus, this work aims to improve the ionic conductivity
Nicolet iS10) was used in the wavenumber range from 4000
and electrochemical properties of PVA based polymer elec-
to 450 cm1 and with having 2 cm1 resolutions.
trolyte, doped with ammonium thiocyanate (NH4SCN):Cu
A Hitachi SU8220 was used to conduct the field emission
(II)-complex and plasticized with various amount of glycerol
scanning electron microscopy (FESEM) at 500
(GLY). Then, the highest conducting sample will be used as
magnification. FESEM images were taken to consider the
polymer electrolyte in the fabrication of EDLC, and the per-
CPE films morphology.
formance of the device will be explored.
The pure PVA and CPE impedance spectra were accom-
plished using electrochemical impedance spectroscopy (EIS)
2. Materials and methods
[3532–50 LCR HiTESTER (HIOKI)] in the frequencies
between 50 Hz and 5 106 Hz. The synthesized CPE films
2.1. Materials were cut for circles with 20 mm in diameter as well as located
between stainless steel (SS) electrodes under pressure of a
Sigma-Aldrich (Kuala Lumpur, Malaysia) provided poly(vinyl spring. The CPE samples were linked to a computer program
alcohol) (PVA) powder (average molecular weight = 85000– to consider real (Z’) and imaginary (Z‘‘) parts of the complex
124000), copper(II) chloride (molecular weight = 134.45 g/m impedance (Z*) spectra.
arabjc.2020.08.006
4 M.A. Brza et al.
2.4. Electrolyte characterization cleaned using acetone and finally the synthesized homogenous
solution was coated on it by using a doctor blade. Subse-
2.4.1. Ionic transference number analysis quently, the gained AC electrodes were dried-out in an oven
Two types transference number (TNM) were analyzed, which at 60 °C with the mass loading of active material of 2.43 mg.
are ionic (tion) and electronic (tel) TNM. The cell preparation Finally, the dried AC electrodes were kept in a dessicator with
arrangement was SS| highest CPE (PGNC-4)| SS. The cell silica gel for drying better. The formed electrodes were cut into
was connected to a V&A Instrument DP3003 digital DC circles with area of 2.01 cm2. The mass of electrode minus with
power supply and a UNI-T UT803 multimeter. The circuit dia- the mass of aluminum foil was 2.99 mg. From the mass men-
gram for the TNM measurement is shown in Fig. 2. The cell tioned earlier, AC was 81.25% from the total mass of each cir-
polarized versus time at the working voltage of 0.2 V and cle electrode. Hence, the mass of AC was 2.43 mg and was to
ambient temperature. tion and tel can be calculated from Eqs. calculate EDLC parameters because AC is the active mass.
(1) and (2) (Ramesh et al., 2011):
Ii Iss 2.6. EDLC characterization
tion ¼ ð1Þ
Ii
The AC electrodes were cut into circles with area of 2.01 cm2.
tel ¼ 1 tion ð2Þ The utmost conducting PE (PGNC-4) was set in between two
Here initial current and steady-state current are designated AC electrodes and laid in a CR2032 coin cell. Finally, the coin
as Ii and Iss, correspondingly. cell was located in a Teflon case as exhibited in Fig. 3.
The cyclic voltammetry (CV) of the EDLC was taken with
2.4.2. Linear sweep voltammetry (LSV) Digi-IVY DY2300 potentiostat. The applied potential was in
the range between 0 V and 0.9 V with various scan rates.
In order to check the electrochemical stability of the prepared The EDLC displayed in Fig. 3 was exposed with several scan
CPEs before the EDLC fabrication, the linear sweep voltam- rates of 5, 10, 20, 50, and 100 mV s1. The specific capacitance
metry (LSV) investigation was accomplished. The cell arrange- CCV of the EDLC at the several scan rates can be developed
ment for the LSV is similar to the TNM examination in Fig. 2. from the CV profile through the following relation (Asnawi
Scan rate of 10 mV s1 was given from 0 to 2.5 V at ambient et al., 2020):
temperature. The cell was linked to the working electrode, ref-
erence electrode, and counter electrode by means of Digi-IVY Z Vf
IðVÞdV
DY2300 potentiostat. When potential was swept linearly CCV ¼ ð3Þ
Vi 2mv Vf Vi
between working electrode and counter electrode, the change
in the current value at the working electrode was recorded. R
The cell setup for the LSV test is displayed in Fig. 2. The CV plot area ( IðVÞdV) can be acquired using function
of integration in Origin 9.0 software. v refers the scan rate, m
2.5. EDLC fabrication refers the mass of activated carbon (2.43 mg), Vf and Vi are the
final voltage of 0.9 V and the initial voltage of 0 V, respec-
tively. The EDLC rechargeability is checked via NEWARE
Planetary ball miller (XQM-0.4) was employed to mix the
battery cycler for 1000 cycles at a current density of
0.25 g of carbon black and 3.25 g of activated carbon (AC)
0.5 mA cm2 or 0.33 mAg1. The surroundings for analysis
at 500 rpm for around 20 min. Six metal balls were incorpo-
the CV and EDLC charge–discharge was settled at ~25 °C
rated to a chamber together with the above powders. Then,
and relative humidity of ~50%. The specific capacitance (Cd)
0.5 g of polyvinylidene fluoride (PVdF) was inserted in the sol-
using discharge curve can be found from Eq. (4) (Asnawi
vent of 15 mL N-methyl pyrrolidone (NMP) and then stirred
et al., 2020):
for around 60 min. The powders were transferred into the
PVdF-NMP solution and then stirred for 2 h till the emergence i
Cd ¼ ð4Þ
of homogenous solution of dense black. An aluminum foil was xm
Fig. 2 Illustration of TNM experimental system. Fig. 3 Design of the synthesized EDLC.
arabjc.2020.08.006
Here i and denote applied current and gradient of dis- nearly 2h = 20◦ and 40◦ in the XRD spectrum of pure PVA
charge part, respectively. The CCV and Cd values of the EDLC are noted, which have been related to the crystalline structure
were compared so as to check the confidence of the results. The of PVA in previous investigations (Hema et al., 2008;
situation of the contact between the electrode and CPE of the Hemalatha et al., 2019). It is clear that these peaks still exist
EDLC device was validated by means of the following equa- in the XRD spectra of PVA:NH4SCN:Cu(II)-complex:GLY
tion (Asnawi et al., 2020): even though their intensities were considerably decreased.
Vd More explicitly, the peak at 2h = 40◦ almost disappeared,
ESR ¼ ð5Þ whereas the peak at 2h = 20◦ widened. The extension of the
i
amorphous nature is ascribed in the wideness increase and fall
where ESR denotes equivalent series resistance and Vd denotes in the peak intensity at 2h = 20◦ (Aziz et al., 2017; Aziz, 2016).
potential drop before discharging process. The doping of salt to the host polymer is probable to raise
the structure of amorphous nature in PE. In an earlier
3. Results and discussion research, the XRD pattern of starch-chitosan:NH4Cl SPE sys-
tem showed a clear increase in the crystalline peaks with
3.1. XRD examination emerging additional crystalline peaks at maximum salt concen-
tration (Shukur and Kadir, 2015). This outcome designated
The XRD pattern of pure PVA and PVA:NH4SCN:Cu(II)- the salt recrystallization and ions recombination, which
complex:GLY are displayed in Fig. 4. A couple of peaks at resulted in the decrement of free ions density, and therefore
declined the rDC (Shukur and Kadir, 2015). Different
approaches were specified to overcome these challenges. One
of the approaches is the addition of Cu(II)–complex to the
PE in order to develop the amorphous structure and increase
the rDC. The addition of GLY to the electrolyte was also
attempted to further improve the rDC. The amorphous struc-
ture in the electrolyte complexes can be enhanced with the
inclusion of GLY (Amran et al., 2016). The existence of
GLY in the complex systems helps salt dissociation, which in
turn restricts salt recrystallization. Moreover, the plasticizer
can produce different pathways for ions conduction; therefore,
assisting the polymers to accommodate more salt. These pro-
cesses raise the amorphous phase in the PEs, subsequently
enhancing the electrolyte rDC (Shukur and Kadir, 2015). The
ion conduction is desirable in the amorphous structure owing
to segmental movement of polymer chains (Noor and Isa,
2015; Salleh et al., 2016). Moreover, the absence of any
XRD peaks associated with pure PVA, approves the whole
dissociation of NH4SCN salt in the PE (Noor and Isa,
2015). The elimination of hydrogen bonding among the poly-
mer chains causes broadening and weakening in intensity,
which signifies the dominance of the amorphous phase in the
PE system (Hema et al., 2008).
The addition of GLY and Cu(II)–complex will result in the
intensity reduction of crystalline peaks and vanishes the crys-
talline peak at 2h = 20° (see Fig. 4). In our previous work,
it was shown that when Cu(II)-complex was added to the
PVA host polymer, the amorphous nature expanded, which
was noted as a decrease in the intensity of the XRD spectra
(Brza et al., 2019). The Cu(II)-complex XRD pattern in our
earlier work indicated that the prepared Cu(II)-complex is
nearly amorphous, thus the crystalline peaks cannot be per-
ceived through the whole range of 2h degrees. Obviously, just
a hump can be seen from 2h = 20◦ to 30◦ (Brza et al., 2019).
The XRD analysis results approve that a good complexation
took place between the PVA and the electrolyte components.
The deconvolution technique for the XRD spectra was used
to determine the potential amorphous peaks and the crystalline
peaks and it was also used to determine the degree of crys-
tallinity (Xc) (Salleh et al., 2016), as shown in Fig. 4. The large
and wide peaks signify the amorphous peaks, while the nar-
row, sharp and small peaks indicate the crystalline peaks. Pure
Fig. 4 XRD spectra for (a) pure PVA, (b) PGNC-1, (c) PGNC- PVA possesses Xc of 41.68, which is noticeably decreased when
2, (d) PGNC-3, and (e) PGNC-4 films. GLY is inserted. Thus, the amorphous structure of the systems
arabjc.2020.08.006
6 M.A. Brza et al.
is enhanced with the GLY insertion. It is seen in Fig. 4 that (II)–complex on the functional groups of the PVA is the two
when GLY is added, crystalline peaks in PGNC-1 became endorsed clarifications for the band intensity reduction (Brza
smaller and less sharp (Fig. 4 (c-e)). The addition of GLY et al., 2019). Consequently, since adsorption causes an increase
with 40 wt% gives rise to the smaller crystalline peaks, as seen in the molecular weight, there is a reduction in the functional
in the XRD pattern of PGNC-4 (Fig. 4(e)). Eq. (6) was used groups vibrational intensity (Aziz et al., 2017).
to obtain Xc for pure PVA and doped PVA and the Xc values In the meantime, O–H stretching vibration of hydroxyl
are tabulated in Table 1. PGNC-1 system has Xc value of 8.93 (OH) groups can be related with the wide and robust absorp-
while PGNC-4 has the minimum Xc value of 3.54, meaning tion peak at 3340 cm1 (Makled et al., 2013). This band pos-
that the PGNC-4 is the highest amorphous system in this study sesses a high intensity, almost certainly owing to the robust
(Salleh et al., 2016). intra and inters kinds of hydrogen bonding (Hema et al.,
AC 2008). Additionally, this band shifts and peak intensity drops
Xc ¼ 100% ð6Þ in the PVA:NH4SCN:Cu(II)-complex:GLY owing to its com-
AT
plexation with NH4SCN salt and Cu(II)-complex. The peak
Here, AT and AC refer the total area of the amorphous and at around 1643 cm1 in the pure PVA is believed to be origi-
crystalline peaks and total area of the crystalline peaks, respec- nated from the C = O stretching of acetate group
tively, which were accomplished by the deconvolution method (Kharazmi et al., 2015), in which for the doped PVA films it
using the OriginPro software. The Gaussian function mode is shifted to a smaller wavenumber. C–H asymmetric stretch-
was employed for the fitting of the XRD spectra. ing vibration is related with a band at 2913 cm1 (Makled
et al., 2013), which also shifted and reduced considerably in
3.2. FTIR analysis the case of doped PVA films. Furthermore, the characteristic
of –C–O– stretching vibration in pure PVA is ascribed through
The FTIR spectra for pure PVA and PVA:NH4SCN:Cu(II)- the peak at 1076 cm1 (Jiang et al., 2015), which is shifted with
complex:GLY are shown in Fig. 5. The following modifica- dropped intensity in the doped films with Cu(II)-complex and
tions in the spectral features have been detected after compar- GLY, as shown in Fig. 5a.
ing the spectra of pure and doped PVA. C–H rocking of pure The C–H bending vibration of CH2 wagging has been rec-
PVA is considered the reason for absorption peak at 838 cm1 ognized as the cause for the pure PVA absorption peak at
(see Fig. 5a,) (Hema et al., 2008). In the case of PVA:NH4- 1419 cm1, while C–H deformation vibration has been related
SCN:Cu(II)-complex:GLY, this peak shifted and its intensity with the 1317 cm1 absorption peak in pure PVA (see Fig. 5a,)
decreased; whereas, upon the addition of 40 wt% of GLY it (Kharazmi et al., 2015). It is therefore clear that the PVA:NH4-
nearly vanished. SCN:Cu(II)-complex:GLY samples were related with shifting
It is well-known that in NH4SCN salt–polymer, the charge of these two peaks and a considerable reduction in the inten-
carrier species are hydrogen ions (H+) (Srivastava et al., 1995). sity of these peaks. These modifications in the FTIR spectra
The new strong and intense peak detected at 2045 cm1 is are strong evidences for the interaction of PVA functional
endorsed to aromatic S–C = N stretching of anion of SCN- groups with the electrolyte components (see Fig. 5a, b).
group of NH4SCN. This band shifts with considerable inten-
sity reduction upon the addition of the higher GLY concentra- 3.3. Morphological study
tion is related to the complexation with PVA functional groups
(see Fig. 5b) (Hemalatha et al., 2019; Noor and Isa, 2015). In Fig. 6a(i-iv) illustrates surface morphology of all the studied
the ammonium ion NH+ 4 tetrahedral, since just one of the four films through FESEM images. It is recognized that the surface
protons (H+) weakly linked to the nitrogen atom; thus, the morphology of the PE films is the key properties to recognize
H+ will transfer to every coordinating site of PVA. The change their behavior (Aziz et al., 2019). The images were obtained at
in peak place with the emergence of the new peak in the PVA: 500 magnification. The small grey lumps can be seen on the
NH4SCN:Cu(II)-complex:GLY indicates the complex creation surface of the CPE films (see Fig. 6a(i)). These lumps were
amongst the PVA and the NH4SCN (Hemalatha et al., 2019). attributed to the protrude salts. It is evident from the images
The insertion of plasticizer helps further ions dissociation; that the grey lumps are disappeared as the GLY concentration
therefore, additional ions are offered to create interactions was increased from 20 to 40 wt%. The CPE has a smooth and
with the functional groups of PVA (Liang et al., 2009). Fur- uniform surface morphology without existing a phase separa-
thermore, the interaction between PVA functional groups tion as shown in Fig. 6a(ii-iv). It is well documented that
and Cu(II)–complex was indicated in our previous work smooth morphology appearance is related to the amorphous
(Brza et al., 2019). This interaction or the adsorption of Cu phase of the PE system (Mobarak et al., 2013). The smooth
surface electrolytes can assist conducting ionic species to pass
more easily, and therefore increases the value of rDC
(Mobarak et al., 2013). Likewise, the CPE samples with uni-
Table 1 The degree of crystallinity from deconvoluted XRD form surface in Fig. 6a(ii-iv) indicates the fine dispersion of
analysis. Cu(II)-complex. The small white spots appearing on the CPE
Electrolyte Degree of crystallinity (%) films surface are attributed to Cu(II)-complex.
Pure PVA 41.68 This was though, certified to be different in previous works,
PGNC-1 8.93 while extra agglomerated particles on the surface of the CPE
PGNC-2 7.54 films appeared as excessive fillers was included in the polymers.
PGNC-3 5.88 For examples, Hamsan et al. (Hamsan et al., 2017) determined
PGNC-4 3.54 the rDC decrement as more GLY was inserted. It has been
arabjc.2020.08.006
Fig. 5 Spectra of FTIR for (i) pure PVA, (ii) PGNC-1, (iii) PGNC-2, (iv) PGNC-3, and (v) PGNC-4 in the range (a) 450 cm1 to
1900 cm1, and (b) 1900 cm1 to 4000 cm1.
explained that this is ascribed to the rearrangement of self- nearly smooth and uniform without having obvious protruded
linkages of plasticizer producing recrystallization of salt which salts at high GLY concentration. From these outcomes, the
causes a decrease in rDC (Johan and Ting, 2011). Hence, poly- fabricated CPE was well-defined with amorphous behavior
mer capability is restricted to accommodate extra salts, which even at the maximum GLY amount. The role of GYL content
in turn caused recrystallization of salt (Aziz, 2017). Lim et al. on increasing free ionic species in the prepared samples is
(Lim et al., 2014) have also connected the surface morphology schematically illustrated in Fig. 6b.
of CPEs to the rDC. In their work, a fall in rDC upon addition
of 10 wt% TiO2 has been shown for PVA:LiClO4:TiO2 elec- 3.4. Impedance analysis
trolyte systems. They proposed that this observation is due
to the agglomeration of TiO2. They related this to the fact that, The electrochemical and ion transference behaviors of ionic
the CPE surface morphology possesses great level of rigidity materials, for example electrodes and PEs, can be efficiently
owing to the addition of 10 wt% TiO2. Thus, these agglomer- examined by the use of electrochemical impedance spec-
ations could block conducting pathways for ionic movements. troscopy (EIS) (Cho et al., 2015; Svensson et al., 2005). In this
Large rigidity in the back bone of polymer also decreases the work, EIS was used to analyze the impedance plots for the
ion mobility. Consequently, the rDC is reduced with the block- CPE films (see Fig. 7(a-d)). For PGNC-1 system in Fig. 7a,
ing impact and ion transportation is limited. a semicircle at high frequency region is resulted from the CPEs
It is believed that so as to accomplish high rDC, the surface bulk effect, and a tail at low frequencies can be noted. The tail
has to be smooth uniform. In other words, it is linked to the at the low frequencies happens because of the creation of the
film amorphous structure (Kadir et al., 2018). The addition EDLC through the free charges buildup at the electrode and
of Cu(II)-complex improved the amorphous phase further as electrolyte interface (Aziz et al., 2010). The spike or tail was
shown in our previous work (Brza et al., 2019). In fact, the only displayed by the other samples (see Fig. 7(b-d)).
interaction between the PVA and electrolyte’s components is The electrical equivalent circuit (EEC) method is used as a
evinced by the smooth uniform surface morphology of the straightforward way for the EIS examination, which provides
CPE samples (see Fig. 6a(i-iv)). the entire image of electrolyte system (Pradhan et al., 2011).
In this study, the outcomes display that there is an innova- The Nyquist plot for the systems was deduced in terms of
tion of the PE preparation as a novel and simple technique to the EEC. It comprises bulk resistance (Rb) for the carriers in
get a great rDC and high performing EDLC. The FESEM the electrolyte systems and two constant phase elements
images are in good agreement with the XRD and FTIR results. (CPE) as seen in the insert of Fig. 7. The region of high fre-
From the XRD and FTIR routes, the interaction among the quencies displays the connection of Rb and constant phase ele-
PVA and electrolyte’s components were validated. It is indi- ment in parallel, while the region of low frequencies indicates
cated that the CPE surface morphology is observed to be only constant phase element, meaning that the formed EDLC
arabjc.2020.08.006
8 M.A. Brza et al.
Fig. 6 (a) Field emission scanning electron microscopy (FESEM) for (i) PGNC-1, (ii) PGNC-2, (iii) PGNC-3, and (iv) PGNC-4
electrolytes. (b) Schematic illustration of the role of GYL content on ion dissociation.
between electrode and electrolyte. The constant phase elements 1 h pp ppi
ZCPE ¼ p
cos isin ð7Þ
term is more usually employed in EEC rather than ideal capac- Cx 2 2
itor in the real system.
The impedance of ZCPE can be written as (Hamsan et al., where C stands for the constant phase element capacitance, x
2017; Aziz and Abdullah, 2018): refers the angular frequency and p is linked to the departure of
arabjc.2020.08.006
Fig. 7 Experimental EIS for (a) PGNC-1, (b) PGNC-2, (c) PGNC-3, and (d) PGNC-4 electrolyte films.

the EIS plots from the vertical axis. Here, the real (Zr) and sin pp22
Zi ¼ ð11Þ
imaginary (Zi) parts of complex impedance (Z*) correlated C2 xp2
with the EEC (insert of Fig. 7a) are indicated as (Aziz and
Table 2 outlines the fitting parameters of the EEC. The Rb
Abdullah, 2018):
is obtained by the interception between the real axis and the
spike. It is obvious that upon the addition of the GLY, the
Rb C1 xp1 cos pp21 þ Rb cos pp22
Zr ¼ Rs þ þ ð8Þ semicircle at the region of high frequencies were absent (see
2Rb C1 xp1 cos pp21 þ Rb 2 C1 2 x2p1 þ 1 C2 xp2
Fig. 7b-d) due to the complete transport of ions toward the
electrodes. The Rb is dropped as the GLY amount increases
Rb C1 xp1 sin pp21 sin pp22 to 40 wt% because of the increase in mobility of charge spe-
Zi ¼ þ ð9Þ
2Rb C1 xp1 cos pp21 þ Rb 2 C1 2 x2P1 þ 1 C2 xp2 cies, ensuring the rise in the rDC of ions. The increase in rDC
with the GLY amount is consistent with the FESEM results
where C1 refers the bulk constant phase element capacitance (see Fig. 6). The addition of Cu(II)–complex to the PE signif-
and C2 refers the constant phase element capacitance at the icantly promoted the amorphous nature that caused to
interface of electrode and electrolyte. increase the rDC and improve the EDLC performing. Ran-
Here, the Zr and Zi parts of Z* associated with the EEC (in- gasamy et al., (Rangasamy et al., 2019) thought that the
set of Fig. 7b-d) are expressed as (Aziz and Abdullah, 2018): increase in the amorphous phase of the PE increases the ions

cos pp22 mobility by developing more free volume in the PE system.
Zr ¼ Rs þ ð10Þ This leads to an increase in the polymer chains segmental
C2 xp2
arabjc.2020.08.006
10 M.A. Brza et al.
Table 2 The fitting parameters of the EEC for CPEs system at room temperature.
Sample P1 (rad) P2 (rad) K1 (F-1) K2 (F-1) C1 (F) C2 (F)
PGNC-1 0.814768 0.383195 1.20 109 9.20 104 8.33 10-10 1.09 10-5
PGNC-2 – 0.668364 – 8.60 104 – 1.16 10-5
PGNC-3 – 0.706885 – 3.20 104 – 3.13 10-5
PGNC-3 – 0.681095 – 2.27 104 – 4.41 10-5
motion, due to the rise in the polymer chains flexibility. There- decrease until it gets saturation. The current polarization set
fore, the rDC in the PE can be improved. Liew (Liew, 2017) against time for the maximum conducting CPE (PGNC-4) is
had developed the CPE based on PAA:LiTFSI with the inser- portrayed in Fig. 8. The cause for the enormous of the early
tion of BaTiO3. The author obtained rDC of 5 10–4 S cm1 current value is in consequence of the part held by the ion
and used the CPE in the EDLC cells. This indicates that CPE and the electron carriers at the early stage. Fig. 8 illustrates
is a good candidate to be employed as a PE in the EDLC that there is a substantial reduction in the current prior it
device. By considering the Rb value and the CPE dimensions, reached an equilibrium state. Once the CPE was polarized, it
the rDC of the CPE films can be calculated using the relation is in the equilibrium; whereas, the maintained current move-
below (Aziz et al., 2019); ment is owing to electron species. The cause for that is the
blocking of ions caused by the SS electrodes, which lets only
1 t
rdc ¼ ð12Þ the electron to transport through it (Rani et al., 2018). Eqs.
Rb A
(1) and (2) are employed to evaluate tion and tel values, which
where t denotes the CPE thickness. A refers to the area of the obtaining Ii and Iss values as 279.9 mA and 8.1mA, respectively.
SS electrode. The values of rDC of the CPE samples are listed The tion and tel values are established to be 0.971 and 0.029,
in Table 3. Previous reports have indicated that PEs with high respectively. It is interesting to note that the tion is very close
rDC in the range between 10-5- 10-3 S cm1 can be employed to the ideal value of one. Subsequently, it is concluded that
for use in EDLCs (see Table 4). The rDC value of the synthe- ions have a significant role in the transportation mechanism
sized EDLC is in comparison with previous works using a in the PVA:NH4SCN:Cu(II)–complex:GLY system.
number of PEs as recorded in Table 4. The idea of rDC value
was supported in the sense that the rDC depends on the charge 3.5.1.1. Electrochemical stability study. The electrochemical
number density (ni) as well as ionic mobility (mi), as follows stability window (ESW) is an essential characteristic to be
(Aziz, 2013); studied (Pandey et al., 2010). Hence, linear sweep voltammetry
X (LSV) measurement is led to find the PE decomposition volt-
rdc ¼ ni qi li ð13Þ age. The device performance is verified when one is alert of
i
the ESW of the PE film prior the test of charge–discharge
Here qi stands for the charge of the species (1.6 1019C). cycles. To avoid causing any harm to the PE, the decomposi-
There was an increase in rDC when ni and mi inside the system tion voltage is vital. Fig. 9 depicts the LSV plot of PGNC-4
of PE increases, as it is apparent from Eq. (13). The Table 3 at 10 mV s1 with a voltage range of 0 to 2.5 V. There is no
data as well as EIS spectra in Fig. 7 obviously indicate that obvious change in the current within the working electrode
having more GLY concentration will give rise to the value of in the voltage varying from 0 to 2.15 V. ESW is observed at
rDC. GLY decreases the attraction force between the cations 2.15 V as the current starts to raise drastically, revealing
and anions of the salt (Shukur and Kadir, 2014, 2015). Thus, CPE decomposition.
a greater number of ammonium ions (ni) is offered by NH4- This outcome is similar to the work by Liew (Liew, 2017)
SCN to the polymer. on PAA:LiTFSI:BaTiO3 CPE with ESW of 2.3 V. They
employed the CPE in an EDLC. Kadir & Arof (Kadir and
3.5. EDLC characteristics Arof, 2011) reported that the ESW for PVA-chitosan-
NH4NO3-EC film is 1.70 V, which is lesser than the obtained
3.5.1. Transference number measurement (TNM) result in our work. The usual ESW for protonic battery use
TNM is employed to identify the highest carrier species inside is approximately 1 V (Pratap et al., 2006). Therefore, the
the CPE. When 0.2 V is applied, the current commences to decomposition voltage of PGNC-4 highlights its suitability
for applications in protonic devices. Lim et al. (Lim et al.,
2014) documented that the decomposition voltage of PVA:
Table 3 Achieved rDC of the PVA:NH4SCN:Cu(II)-complex: LiClO4:TiO2 was found to be 2.4 V and they used the CPE
GLY system at room temperature. in an EDLC.
Designation Composition (PVA wt. Rb rDC
%:NH4SCN wt.%:Cu (Ohm) (S cm1) 3.5.1.2. Cyclic voltammetry study. Cyclic Voltammetry (CV)
(II)–complex mL:GLY examination was employed to assess the performance of
wt.%:) EDLC using PGNC-4 CPE. Fig. 10 shows the CV plot of
PGNC-1 50:50:10:10 2.28 104 5.23 10-7
EDLC at various scan rates of 5, 10, 20, 50, and 100 mV s1.
PGNC-2 50:50:10:20 50 3.24 10-4 No peak is seen in the CV plot signifying that no redox reac-
PGNC-3 50:50:10:30 12 1.46 10-3 tion happens at the potential range of 0 to 0.9 V. This is veri-
PGNC-4 50:50:10:40 11 2.25 10-3 fied the existence of EDLCs (Liew and Ramesh, 2015). As seen
in Fig. 10, the CV plot shape deviated from a leaf shape to a
arabjc.2020.08.006
Table 4 DC conductivity (rDC) specific capacitance (Cd), energy density (Ed), power density (Pd), and cycle number of EDLCs using
dissimilar PEs at room temperature.
Electrolyte composition rDC (S cm1) Cd (F Ed (Wh Pd (W Cycle Ref.
g1) kg1) kg1) No.
PVA:LiClO4:TiO2 1.3 10-4 12.5 1.56 198.7 1000 (Lim et al., 2014)
CMC:KC:NH4NO3 ~10-4 20 – – 10,000 (Zainuddin et al., 2020)
Chitosan:H3PO4:NH4NO3: (1.82 ± 0.1) 10-4 0.2 – – 100 (Arof and Majid, 2008)
Al2SiO5
PAA:LiTFS:BaTiO3 5 10–4 34.22 3.32 71.47 20,000 (Liew, 2017)
PDMA: MgTf2: Co3O4 9.4 10–3 29.48 1.89–2.62 157.7–240.4 8000 (Bashir et al., 2020)
Dextran:NH4Br (1.67 ± 0.36) 106 2.05 – – 100 (Hamsan et al., 2020)
PS:MC:NH4NO3:GLY ~103 31 3.1 910–385 1000 (Hamsan et al., 2017)
PVA:chitosan:NH4NO3:EC 1.6 10-3 27.1 – – 100 (Kadir and Arof, 2011)
MC:NH4Br:GLY (1.89 ± 0.05) 104 – – – - (Kadir et al., 2018)
Chitosan:MC:NH4I 6.65 104 9.97 1.1 578.55 100 (Aziz et al., 2020)
PVA:Naft:BmImBr 2.31 103 16.32 – – 1000 (Farah et al., 2019)
Chitosan:MC:NH4F 2.96 10-3 58.3 7.3 964 100 (Aziz et al., 2020)
PVA:CH3COONH4:BmImBr (9.29 ± 0.01) 103 21.89 1.36 34.66 500 (Liew et al., 2015)
PVA:dextran:NH4I 2.08 105 4.2 0.55 64 100 (Aziz et al., 2020)
MC:NH4NO3:PEG 38 3.9 140 100 (Shuhaimi et al., 2012)
MC:dextran:NH4I 1.12 103 79 8.81 1111.1–170 100 (Aziz et al., 2020)
Cellulose acetate:LiClO4 4.9 103 90 – – 600 (Selvakumar and Bhat,
2008)
EMIM-TFSI:PVDF-HFP – 51.8 15.7 1048 3000 (Lee et al., 2014)
PVA:NH4SCN:Cu-complex:Gly 2.25 10-3 155.32 17.473 4960 1000 This work
Where; LiClO4 = Lithium perchlorate, TiO2 = Titanium dioxide, CMC = Carboxymethyl cellulose, KC = kappa carrageenan, NH4-
NO3 = Ammonium nitrate, Al2SiO5 = Aluminium silicate, PAA = Poly(acrylic acid), LiTFS = lithium bis(trifluoromethanesulfonyl)imide,
BaTiO3 = barium titanate, PS = Potato starch, MC = methylcellulose, EC = ethylene carbonate, CH3COONH4 = Ammonium acetate,
BmImBr = 1-butyl-3-methylimidazolium bromide, PEG = poly (ethylene glycol), EMI-TFSI = 1-ethyl-3-methylimidazolium bis(trifluo-
romethanesulfoly) amide, PVdF = poly(vinylidene fluoride), HFP = hexafluoropropylene, PDMA = poly (N, N-dimethylacrylamide),
MgTf2 = Magnesium trifluoromethanesulfonate, Co3O4 = Cobalt oxide, Naft = sodium trifluoromethanesulfonate, BmImBr = 1-butyl-3-
methylimidazolium bromide, NH4F = Ammonium fluoride.
Fig. 9 LSV plot for the maximum conducting (PGNC-4) CPE

Fig. 8 Polarization current versus time for the maximum film.
conducting (PGNC-4) CPE film.
Lim et al. (Lim et al., 2014). In their study, the CV at the scan
nearby shape of a rectangle when the scan rate decreases. High rates of 10, 30, 50, and 100 mV s1 were created for EDLCs
scan rate causes a departure of the CV plot from rectangular with the system of PVA:LiClO4:TiO2-based CPE.
shape that is ascribed to the internal resistance and carbon
porosity; hence, generating a current–voltage dependence 3.6. Galvanostatic charge–discharge analyses
(Kadir and Arof, 2011). The values of CCV will be derived
from the profile of CV with Eq. (3) and are presented in Table 5
at different scan rates of 5, 10, 20, 50, and 100 mV s1. The Fig. 11a displays the EDLC charge–discharge profile at initial
value of CCV increases as the scan rate drops. Ions use the cycles at 0.5 mA cm2 current density. The roughly discharge
whole vacant sites through the electrodes where ions have curves with linear slope designates the EDLC capacitive man-
appropriate time for the mechanism of diffusion at short scan ners (Lim et al., 2014). The charge–discharge plot of the EDLC
rates, causing in grander value of CCV (Lim et al., 2014). The at 0.5 mA cm2 for the selected cycles up to 1000th cycles is
CV shapes acquired in this work is similar to that achieved by exposed in Fig. 11b, c. It could be seen that the discharge slope
arabjc.2020.08.006
12 M.A. Brza et al.
of the electrodes and electrolytes that causes greater Cd value

of EDLC (Liew, 2017).
The decrease in the voltage throughout the discharging pro-
cess is caused by the EDLC internal resistance. The low drop
voltage value, Vd, in this study denotes that less energy is dis-
sipated during the charge–discharge process. The value of Vd is
found by using Eq. (5) and displayed in Fig. 13. It can be seen
that the increase in the value of Vd is still small throughout
1000 cycles, revealing the high performance of the fabricated
EDLC. The EDLC internal resistance is attributed as equiva-
lent series resistance (ESR). Therefore, a low ESR is crucial for
the EDLC application. As documented by Arof et al. (Arof
et al., 2012), the ESR in the EDLC is originated from the resis-
tance of the current collectors, PE, and the space amongst the
Fig. 10 Cyclic voltammetry (CV) plot of the synthesized EDLC
PE and the current collector. ESR is determined via Eq. (5),
for the largest conducting (PGNC-4) CPE film.
and the values are illustrated in Fig. 14. A best contact among
PEs and electrodes would be achieved because of low ESR,
meaning that the migration of ions to the pores at the elec-
is still almost linear, signifying the presence of capacitive trodes surface would be efficient (Asmara et al., 2011). Kumar
behavior of the EDLC (Lim et al., 2014). Fig. 11b,c displays & Bhat (Kumar and Bhat, 2009) documented that the increase
the charge–discharge performance of the EDLC at specific in Vd among the cycles of charge–discharge, which creates the
cycles. At the beginning of charge–discharge process more ions increase in ESR is caused by the PE degradation in the EDLC.
are available to form double layer thus providing longer dis- Fortunately, the increase in the ESR of the EDLC in the cur-
charge time. As the cycle number increase, the discharge time rent work is still small within 1000 cycles. The ESR in the cur-
become shorter, this is due to recombination of ion to form ion rent study is much lower than the ESR values documented for
pairs or triplets. The development of ion pairs reduces the other EDLC devices (Zainuddin et al., 2020; Aziz et al., 2020).
charge double-layer. The energy density (Ed) and power density (Pd) of the
The value of Cd is computed by substitution the value of the EDLC device are achieved using the following equations
slope of the discharge curves in Eq. (4). Fig. 12 displays the Cd (Aziz et al., 2020):
versus number of cycles. The Cd value calculated for the 1st Cs V
cycle is 128.6F g1. This value is analogous to the CCV Ed ¼ ð14Þ
2
obtained from CV examination (see Table 5). Therefore, the
Cd value accomplished from the EDLC in this study is respon- V2
sible. The value of Cd was found to increase and stays constant Pd ¼ ð15Þ
4mðESRÞ
with the average of 155.32F g1 besides the 1st cycle till it fin-
ishes 1000 cycles. Though, in previous documents significant where V denotes the used voltage.
decrease of Cd has been discerned with raising the number of From Fig. 15, it can be perceived that the value of Ed using
cycles (Lim et al., 2014; Liew, 2017). The achieved Cd in this Eq. (14) for the 1st cycle is 14.467 Wh kg1.The value of Ed
study is much higher than those stated in the literature using exhibits an increase and continues constant with the average
various PEs (see Table 4). of 17.473 Wh kg1 within the cycles beyond the 1st cycle up
The development of Cd in the EDLC is ascribed to the to 1000 cycles. It means that the same energy barrier is sub-
higher rDC value of the CPE due to the influence of the Cu jected by ions species in migration to the surface of the AC
(II)-complex on the enhancement of the amorphous structure electrodes for the processes of charge–discharge within 1000
(Brza et al., 2019), and the addition of GLY plasticizer cycles. Though, in previous reports noticable decrease in Ed
(Hamsan et al., 2017). As reported by Fan et al. (Fan et al., value were noted with increasing the cycle number (Liew,
2018), the development of the amorphous phase is to be bene- 2017; Liew et al., 2015). They described that the decrease in
ficial in local chain segmental motion that can encourage the the value of Ed within the cycle number is ascribed to the raise
ions transportation and hence increasing the rDC. Thus, ions in the ESR that creates the increase of energy loss through the
can transfer freely through the PE. Fast ion migration in the mechanism of charge–discharge cycles (Kadir and Arof, 2011;
CPE also encourages the adsorption of ions at the interfaces Wei et al., 2005). The accomplished Ed for the EDLC is suffi-
ciently large compared to that described (3 Wh/kg) for PAA:
LiTFSI:BaTiO3- based CPE (Liew, 2017). The obtained Ed
Table 5 Capacitance values from CV as opposed to scan in the current study is of the considerable attention in respect
rates. of the Ed value of roughly 1.56 Wh/kg that found for EDLC of
the CPE system of PVA:LiClO4:TiO2 (Lim et al., 2014). For-
Scan rates (mv/s) Capacitance (F/g)
tunately, the value of Ed (17.473 Wh kg1) within 1000 cycles
100 64.014 in the current work is in the range of battery energy density
50 100.137 and significantly higher than the Ed values reported in the lit-
20 123.457
erature (see Table 4). These results indicate that the Cu(II)-
10 132.602
5 134.889
complex as filler has a great impact on the performance of
the EDLC device.
arabjc.2020.08.006
Fig. 11 Charge–discharge profiles for the synthesized EDLC at 0.5 mA cm2 for (a) initial cycles, (b) selected cycles of 100th, 200th,
400th, 600th, 700th, and 1000th and (c) selected cycles of 100th, 500th, and 1000th.
arabjc.2020.08.006
14 M.A. Brza et al.
Fig. 16 Pd of the developed EDLC for 1000 cycles.

Fig. 12 Cd of the synthesized EDLC for 1000 cycles.
The achieved Pd value using Eq. (15) for our study will be
seen in Fig. 16. Over charge–discharge within 1000 cycles, the
Pd value for the 1st cycle is 4960 W kg1 and subjected to a
drop up to 500th cycle with the average of 2277 W kg1 and
then continues constant with the average of 400 W kg1
throughout the cycles beyond the 500th cycle. The drop of
Pd at higher cycles is because of the depletion of the PE. Ion
agglomeration after the fast charge–discharge mechanisms
blocks the migration of ions to the electrodes that causes a
decrease of adsorption of ions at the interfaces of the elec-
trodes and PEs (Liew et al., 2016). This tendency of Pd drop
is in agreement with the rising ESR tendency. The ESR raise
at greater cycles due to the reduction in the mobile ion concen-
Fig. 13 Vd pattern of the fabricated EDLC for 1000 cycles. tration and aggregation of ions after the swift processes of
charge–discharge cycles offers smaller Pd at higher cycles
(Zhong et al., 2015). The accomplished Pd for the EDLC cell
is high in comparison to that reported in the literature (see
Table 4).
4. Conclusion
PVA:NH4SCN:Cu(II)-complex:GLY -based CPE was effi-

ciently fabricated using the solution casting process. The addi-
tion of Cu(II)-complex and GLY maximized the rDC up to
2.25 10-3 Scm1. Outcome from the XRD route displayed
that the highest glycerolized CPE exhibits the most amor-
phousity. Outcome from the XRD examination displayed that
the utmost conducting plasticized system has the smallest
degree of crystallinity and the XRD outcomes could also be
associated to the trend in the degree of crystallinity with con-
Fig. 14 ESR pattern of the created EDLC for 1000 cycles.
ductivity variation of the CPE sytems. Using the FTIR route,
the interaction amongst PVA and the PE components was con-
firmed. The FESEM route revealed that the films surface mor-
phology were smooth uniform at higher GLY concentration.
TNM established that the dominant charge carriers were ions.
The tion as well as tel for the utmost conducting CPE were
determined to be 0.971 and 0.029, respectively. LSV route dis-
played that the decomposition voltage for PGNC-4 system is
at 2.15 V, suggesting its appropriateness in the EDLC applica-
tion. Capacitive manner in the synthesized EDLC was con-
firmed by CV examination, as no redox peaks were
perceived. CCV was revealed to be affected by the used scan
rates. The Cd and Ed of the EDLC are almost constant
throughout 1000 cycles with average values of 155.322F/g
and 17.473 Wh/Kg, respectively at a current density of
0.5 mA/cm2. Fortunately, the Ed of the EDLC in the current
Fig. 15 Ed of the synthesized EDLC for 1000 cycles. work is in the range of battery energy density. The low value
arabjc.2020.08.006
of ESR indicates that the EDLC has a proper contact among the Efficiency of a Dye-Sensitized Solar Cell Based on a Metal
the AC electrodes and the PEs. The EDLC has initial high Pd Oxide Nanocomposite Gel Polymer Electrolyte. ACS Appl. Mater.
as 4960.31 W/Kg. Interfaces. 11, 30185–30196. https://doi.org/10.1021/
acsami.9b07062.
Aziz, S.B., Hamsan, M.H., Brza, M.A., Kadir, M.F.Z., Muzakir, S.K.,
Acknowledgments Abdulwahid, R.T., 2020. Effect of glycerol on EDLC characteris-
tics of chitosan : methylcellulose polymer blend electrolytes. J.
The authors appreciatively acknowledge the financial support Mater. Res. Technol. 9, 8355–8366. https://doi.org/10.1016/j.
for this work by the Ministry of Higher Education & Scientific jmrt.2020.05.114.
Research-Kurdish National Research Council (KNRC)- Chong, M.Y., Numan, A., Liew, C.W., Ng, H.M., Ramesh, K.,
Kurdistan Region-Iraq. Ramesh, S., 2018. Enhancing the performance of green solid-state
electric double-layer capacitor incorporated with fumed silica
nanoparticles. J. Phys. Chem. Solids. 117, 194–203. https://doi.
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Arabian Journal of Chemistry (2020) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

Metal framework as a novel approach for the

Received 6 June 2020; accepted 9 August 2020

Production and hosting by Elsevier

1. Introduction An electrolyte film and two porous electrodes are included

Fig. 9 LSV plot for the maximum conducting (PGNC-4) CPE

of the electrodes and electrolytes that causes greater Cd value

Fig. 16 Pd of the developed EDLC for 1000 cycles.

PVA:NH4SCN:Cu(II)-complex:GLY -based CPE was effi-

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