Journal Pre-proofs

Original article

Metal Framework as a Novel Approach for the Fabrication of Electric Double

Layer Capacitor Device with High Energy Density Using Plasticized Poly(vi-
nyl alcohol): Ammonium Thiocyanate Based Polymer Electrolyte

M.A. Brza, Shujahadeen B. Aziz, H. Anuar, Fathilah Ali, M.H. Hamsan,

M.F.Z. Kadir

PII: S1878-5352(20)30285-9
DOI: https://doi.org/10.1016/j.arabjc.2020.08.006
Reference: ARABJC 2763

To appear in: Arabian Journal of Chemistry

Received Date: 6 June 2020

Revised Date: 6 August 2020
Accepted Date: 9 August 2020

Please cite this article as: M.A. Brza, S.B. Aziz, H. Anuar, F. Ali, M.H. Hamsan, M.F.Z. Kadir, 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), doi: https://doi.org/10.1016/j.arabjc.2020.08.006

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Title page

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. Brza1, Shujahadeen B. Aziz2,3,*, H. Anuar1, Fathilah Ali4, M. H. Hamsan5

and M. F. Z. Kadir6

1Department of Manufacturing and Materials Engineering, Faculty of Engineering,

International Islamic University of Malaysia, Kuala Lumpur, Gombak 53100,
Malaysia
2Advanced Polymeric Materials Research Lab., Department of Physics, College of

Science, University of Sulaimani, Qlyasan Street, Sulaimani 46001, Iraq

3Department of Civil Engineering, College of Engineering, Komar University of

Science and Technology, Sulaimani, 46001, Kurdistan Regional Government, Iraq

4Department of Biotechnology Engineering, Faculty of Engineering, International

Islamic University of Malaysia, Kuala Lumpur, Gombak 53100, Malaysia

5Institute for Advanced Studies, University of Malaya, 50603 Kuala Lumpur,

Malaysia
6Centre for Foundation Studies in Science, University of Malaya, 50603 Kuala

Lumpur, Malaysia

*Correspondence: [email protected]

1
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. Brza1,2, Shujahadeen B. Aziz2,3,*, H. Anuar1, Fathilah Ali4, M. H. Hamsan5,

M. F. Z. Kadir6 and Rebar T. Abdulwahid7
1Department of Manufacturing and Materials Engineering, Faculty of Engineering,
International Islamic University of Malaysia, Kuala Lumpur, Gombak 53100, Malaysia.
2Advanced Polymeric Materials Research Lab., Department of Physics, College of Science,

University of Sulaimani, Qlyasan Street, Sulaimani 46001, Iraq.

3Department of Civil Engineering, College of Engineering, Komar University of Science and

Technology, Sulaimani, 46001, Kurdistan Regional Government, Iraq.

4Department of Biotechnology Engineering, Faculty of Engineering, International Islamic

University of Malaysia, Kuala Lumpur, Gombak 53100, Malaysia.

5Institute for Advanced Studies, University of Malaya, 50603 Kuala Lumpur, Malaysia.
6Centre for Foundation Studies in Science, University of Malaya, 50603 Kuala Lumpur,

Malaysia.
7Department of Physics, College of Education, University of Sulaimani, Old Campus,

Kurdistan Regional Government, Sulaimani 46001, Iraq.

*Correspondence: [email protected]

Abstract
High performance electric double-layer capacitors (EDLCs) based on poly (vinyl
alcohol) (PVA): ammonium thiocyanate (NH4SCN):Cu(II)-complex plasticized with
glycerol (GLY) have been fabricated. The maximum DC ionic conductivity (σDC) of
2.25 × 10-3 S cm-1 is achieved at ambient temperature. The X-ray diffraction (XRD)
patterns confirmed that the addition of both Cu(II)–complex and GLY enhanced the
amorphous region within the samples. Through the Fourier 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 agreement 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 window 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 rectangular
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 155.322 F/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.
Keywords: PVA polymer electrolyte; Glycerol plasticizer; Cu(II)-complex;

2
Electrochemical and EDLC.

1. Introduction

Supercapacitors (SCs) can be categorized into three kinds of electrochemical

capacitor (EC) which are known as electric double-layer capacitor (EDLC),

pseudocapacitor, and hybrid SCs. In the EDLC the electric energy is stored based on

electrosorption process (charge-discharge) when the Helmholtz double layers are

formed on porous electrodes through movement of ions inside the electrolyte [1].

Pseudocapacitor stores energy faradaically by chemical interaction between the

electrolyte and electrode for example redox reaction. The process of charge storage

used in hybrid capacitors is a mix of the both faradaic reaction and non-faradaic

reaction. EDLC is the typical non-faradaic SC. The charge-discharge cycles just

involve ions adsorption on the surface of the electrodes. It is promising to attain high

energy density (Ed) and power density (Pd) using EDLC. [2-4]. ECs are devices which

can occupy the spaces between battery and electrostatic capacitor with regard to Ed

and Pd as shown in Ragone plot (see Figure 1). The Ragone plot is a chart employed

for comparing the performance of several energy storage devices for example SCs,

fuel cells, conventional capacitors, and batteries [5]. The achieved Ed in the current

work is 17.473 Wh/Kg throughout 1000 cycles which is in the range of Ed of batteries

(see Figure 1).

An electrolyte film and two porous electrodes are included in the EDLC

device. Mostly carbon-based electrodes are used for creating these SCs [5]. The

different carbon-based electrode materials used in EDLCs are carbon aerogels,

activated carbon (AC), carbon nanotubes, carbon nanosize, graphites, and carbon

nanofibers [6]. AC is used in this study as an electrode because of its high

conductivity, chemical stability, large surface area (>1000 m2g−1), cost effective, and

3
high porosity (>2 nm pore width) [7, 8]. At the same time, the electrolyte can be

liquid electrolyte (LE), solid polymer electrolyte (SPE), gel polymer electrolyte

(GPE) [9]. The SPE outweigh LE in many substantial characteristics such as

electrolyte leakage, better safety, high flexibility, light weight, and excellent thermal

stability [1, 10]. These features can essentially enhance the EDLC electrochemical

performances. Additionally, the increased demand for flexible electronic devices

resulted in an increasing trend of employing polymer hydrogels as the separators and

electrolytes for flexible electrochemical energy storage devices [11]. Compared to

SPE, hydrogel electrolyte consists of elastic crosslinked hydrated polymer chains that

trap water in the interstitial spaces of the polymer matrices mainly by surface tension

[12]. This makes the hydrogel electrolyte appear usually wet, which gives a tough and

soft property to the electrolyte [12].

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 environmental issues [13]. However, the electrical and

mechanical properties of these polymers need enhancement in order to be used in the

energy devices [13]. Various host polymers have been widely investigated in this

field, such as chitosan [14], hydroxylethyl cellulose (HEC) [15], Polyethylene oxide

(PEO) [16], poly(vinyl alcohol) (PVA) [17], methylcellulose (MC) [18], N, N-

dimethyl acrylamide (DMA) [19], and polyacrylamide-co-acrylic acid (PAAC) [20].

Previous studies are shown that both mechanical and electrical properties of PVA can

be considerable enhanced when doped with glycerol (GLY) and different salts such as

calcium chloride (CaCl2) and sodium chloride (NaCl) [21,22].

4
 In this research, poly (vinyl alcohol) (PVA) was preferred as a host polymer

due to its biodegradable capability, low cost, and easy processability. Ammonium

thiocyanate (NH4SCN) was used in the current study as a low lattice energy salt to

deliver H+ to the CPE system [23]. Srivastava et al. [24] have stated that the charge

carrier in PEO combined with NH4SCN is the H+. NH4SCN has low lattice energy of

605 kJ.mol-1 compared to other ammonium salts, such as NH4Br (667 kJ mol-1),

NH4Cl (694.7 kJ mol-1), NH4NO3 (648.9 kJ mol-1), NH4F (834.5 kJ mol-1), NH4I (626

kJ mol-1), etc. [25, 26]. Therefore, it is possible to dissociate it easily into cations and

anions when inserted in water as a solvent. This means, larger number ammonium

ions are offered by NH4SCN to the polymer. The addition of Cu(II)–complex to the

polymer electrolyte (PE) was attempted to improve the performance of the electrolyte

films via establishing an amorphous nature which is crucial for ion transport process.

In this study, glycerol (GLY) was also chosen as an appropriate plasticizer since it

enhances DC conductivity (σDC) because of the existence of three groups of hydroxyl

(OH). It is believed that the high dielectric constant value (ɛr) of 42.5 for GLY can

reduce the attraction force amongst the cations and anions of the salt, and also weaken

the force between chains of the polymers [27, 28].

In our previous study it was revealed that the amorphous structure of PVA

polymer enhanced through the inclusion of Cu(II)–complex [29]. To the best of our

knowledge, no study has been reported in literature regarding the role of metal

complex (e.g. Cu(II)-complex) or metal framework on EDLC performance. Mohamad

& Arof, [30] have fabricated the plasticized system of PVA–KOH–Propylene

carbonate (PC)–Al2O3. The results showed that the samples conductivity could be

significantly increased with raising the PC plasticizer content [30]. Lim et al., [1]

fabricated EDLC device based on AC electrodes and PVA:LiClO4:TiO2. They are

5
noted that the insertion of TiO2 into the PVA–LiClO4 system resulted in the σDC of 1.3

× 10-4 S cm-1 and specific capacitance (Cd) value of 12.5 F g-1. Nonetheless, the Cd of

the CPE is still low and the addition of TiO2 was not significantly enhanced the

electrochemical performances of the EDLC. Thus, this work aims to improve the

ionic conductivity and electrochemical properties of PVA based polymer electrolyte,

doped with ammonium thiocyanate (NH4SCN):Cu(II)-complex and plasticized with

various amount of glycerol (GLY). Then, the highest conducting sample will be used

as polymer electrolyte in the fabrication of EDLC, and the performance of the device

will be explored.

107

106
Capacitors
Power Density (W/kg)

105

104
Supercapacitors
103

102
Batteries Fuel Cells
10

1
0.01 0.1 1 10 100 1000
Energy Density (Wh/kg)

Figure 1. Ragone plot of Ed versus Pd for numerous electrochemical energy storage devices [4].

2. Materials and Methods

2.1 Materials

Sigma-Aldrich (Kuala Lumpur, Malaysia) provided poly(vinyl alcohol) (PVA)

powder (average molecular weight = 85000-124000), copper(II) chloride (molecular

weight = 134.45 g/mol) and GLY (molecular weight = 92.09382 g/mol). HmbG

6
chemicals, EMPLURA, and Timcal provided ammonium thiocyanate (NH4SCN)

(molecular weight = 76.12 g/mol), N-Methyl-2-pyrrolidone (NMP) (molecular weight

= 99.13 g/mol), and carbon black (molecular weight = 12.01 g/mol), respectively.

Magna value delivered both of the polyvinylidene fluoride (PVdF) (average molecular

weight = ~534,000 by GPC) and activated carbon (AC) (RP20) (molecular weight =

12.01 g/mol).

2.2 Electrolyte Preparation

One gram of PVA was dissolved in 40 mL of distilled water. The solution was

stirred using magnetic stirrer at the temperature of 80 oC for around 60 min to prepare

the PVA solution. The PVA solution was then left to cool down to room temperature.

Then, fixed amount of 50 wt.% of NH4SCN were added to the PVA solutions and

stirred constantly with magnetic stirrer at ambient temperature until the salt was fully

dissolved in the PVA polymer solutions. Later, PVA:NH4SCN was included with 10

mL of Cu(II)-complex (synthesis of Cu(II)-complex was described in our previous

work in materials and methods section in ref. [29]. Subsequently, the solutions were

mixed and stirred to obtain a good dispersion of Cu(II)-complex in the solution. After

that, the PVA:NH4SCN:Cu(II)-complex were plasticized with 10, 20, 30, and 40 wt.%

GLY and then the prepared samples were coded as PGNC-1, PGNC-2, PGNC-3, and

PGNC-4, respectively. Finally, the plasticized solutions were stirred and mixed until a

homogeneous solution was reached and then preserved in the plastic Petri dishes and

left for drying at room temperature. For drying better, the fabricated CPE films were

preserved in a dessicator comprising silica gel before characterisations.

7
 2.3 Characterization techniques

X-Ray Diffraction (XRD) spectra were achieved through the use of Empyrean X-

ray diffractometer, (PANalytical, Netherland) with operating voltage of 40 × 103 V

and operating current of 40 × 10-3 A. The CPE films were scanned with a CuKα X-ray

monochromatic radiation at 0.15406 nm wavelength and the 2θ glancing angle was

ranged from 10° to 80° with 0.1° step size.

To study the PVA film as well as CPE films, Fourier Transform Infrared (FTIR)

spectrophotometer (Thermo Scientific, Nicolet iS10) was used in the wavenumber

range from 4000 to 450 cm−1 and with having 2 cm−1 resolutions.

A Hitachi SU8220 was used to conduct the field emission scanning electron

microscopy (FESEM) at 500× magnification. FESEM images were taken to consider

the CPE films morphology.

The pure PVA and CPE impedance spectra were accomplished using

electrochemical impedance spectroscopy (EIS) [3532-50 LCR HiTESTER (HIOKI)]

in the frequencies between 50 Hz and 5× 106 Hz. The synthesized CPE films were cut

for circles with 20 mm in diameter as well as located between stainless steel (SS)

electrodes under pressure of a spring. The CPE samples were linked to a computer

program to consider real (Z') and imaginary (Z") parts of the complex impedance (Z*)

spectra.

2.4 Electrolyte Characterization

2.4.1 Ionic transference number Analysis

Two types transference number (TNM) were analyzed, which are ionic (tion) and

electronic (tel) TNM. The cell preparation arrangement was SS| highest CPE (PGNC-

4)| SS. The cell was connected to a V&A Instrument DP3003 digital DC power

8
supply and a UNI-T UT803 multimeter. The circuit diagram for the TNM

measurement is shown in Figure 2. The cell polarized versus time at the working

voltage of 0.2 V and ambient temperature. tion and tel can be calculated from Eq.s (1)

and (2) [31]:

I i  I ss
tion  (1)
Ii

tel  1  tion (2)

Here initial current and steady-state current are designated as Ii and Iss,

correspondingly.

SS Blocking Electrodes
Ammeter

Electrolyte film
To the recorder

DC Voltage Source

+ -
Switch

Figure 2. Illustration of TNM experimental system.

2.4.2 Linear sweep voltammetry (LSV)

In order to check the electrochemical stability of the prepared CPEs before the

EDLC fabrication, the linear sweep voltammetry (LSV) investigation was

accomplished. The cell arrangement for the LSV is similar to the TNM examination

9
in Figure 2. Scan rate of 10 mV s-1 was given from 0 to 2.5 V at ambient temperature.

The cell was linked to the working electrode, reference electrode, and counter

electrode by means of Digi-IVY DY2300 potentiostat. When potential was swept

linearly between working electrode and counter electrode, the change in the current

value at the working electrode was recorded. The cell setup for the LSV test is

displayed in Figure 2.

2.5 EDLC Fabrication

Planetary ball miller (XQM-0.4) was employed to mix the 0.25 g of carbon black

and 3.25 g of activated carbon (AC) at 500 rpm for around 20 minutes. Six metal balls

were incorporated to a chamber together with the above powders. Then, 0.5 g of

polyvinylidene fluoride (PVdF) was inserted in the solvent of 15 mL N-methyl

pyrrolidone (NMP) and then stirred for around 60 minutes. The powders were

transferred into the PVdF-NMP solution and then stirred for 2 hours till the

emergence of homogenous solution of dense black. An aluminum foil was cleaned

using acetone and finally the synthesized homogenous solution was coated on it by

using a doctor blade. Subsequently, the gained AC electrodes were dried-out in an

oven at 60 °C with the mass loading of active material of 2.43 mg. Finally, the dried

AC electrodes were kept in a dessicator with silica gel for drying better. The formed

electrodes were cut into circles with area of 2.01 cm2. The mass of electrode minus

with the mass of aluminum foil was 2.99 mg. From the mass mentioned earlier, AC

was 81.25% from the total mass of each circle electrode. Hence, the mass of AC was

2.43 mg and was to calculate EDLC parameters because AC is the active mass.

10
 2.6 EDLC Characterization

The AC electrodes were cut into circles with area of 2.01 cm2. The utmost

conducting PE (PGNC-4) was set in between two AC electrodes and laid in a CR2032

coin cell. Finally, the coin cell was located in a Teflon case as exhibited in Figure 3.

Coin cell
Teflon case
bottom
Electrolyte

Stainless steel

Coin cell AC Electrode

top

Figure 3. Design of the synthesized EDLC.

The cyclic voltammetry (CV) of the EDLC was taken with Digi-IVY DY2300

potentiostat. The applied potential was in the range between 0 V and 0.9 V with

various scan rates. The EDLC displayed in Figure 3 was exposed with several scan

rates of 5, 10, 20, 50, and 100 mV s−1. The specific capacitance CCV of the EDLC at

the several scan rates can be developed from the CV profile through the following

relation [32]:

Vf I V dV
CCV   (3)
Vi 2mvV f  Vi 

The CV plot area (∫ I V dV ) can be acquired using function of integration in Origin

9.0 software. v refers the scan rate, m 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, respectively. The

11
EDLC rechargeability is checked via NEWARE battery cycler for 1000 cycles at a

current density of 0.5 mA cm-2 or 0.33 mAg-1. The surroundings for analysis the CV

and EDLC charge-discharge was settled at ~25 °C and relative humidity of ~50%. The

specific capacitance (Cd) using discharge curve can be found from Eq.(4) [32]:

i
Cd  (4)
xm

Here i and x denote applied current and gradient of discharge part, respectively. The

CCV and Cd values of the EDLC were compared so as to check the confidence of the

results. The situation of the contact between the electrode and CPE of the EDLC

device was validated by means of the following equation [32]:

Vd
ESR  (5)
i

Where ESR denotes equivalent series resistance and Vd denotes potential drop before

discharging process.

3 Results and discussion

3.1 XRD Examination

The XRD pattern of pure PVA and PVA:NH4SCN:Cu(II)-complex:GLY are

displayed in Figure 4. A couple of peaks at nearly 2θ = 20◦ and 40◦ in the XRD

spectrum of pure PVA are noted, which have been related to the crystalline structure

of PVA in previous investigations [33, 34]. It is clear that these peaks still exist in the

XRD spectra of PVA:NH4SCN:Cu(II)-complex:GLY even though their intensities

were considerably decreased. More explicitly, the peak at 2θ = 40◦ almost

disappeared, whereas the peak at 2θ = 20◦ widened. The extension of the amorphous

12
nature is ascribed in the wideness increase and fall in the peak intensity at 2θ = 20◦

[35, 36].

The doping of salt to the host polymer is probable to raise the structure of

amorphous nature in PE. In an earlier research, the XRD pattern of starch-

chitosan:NH4Cl SPE system showed a clear increase in the crystalline peaks with

emerging additional crystalline peaks at maximum salt concentration [28]. This

outcome designated the salt recrystallization and ions recombination, which resulted

in the decrement of free ions density, and therefore declined the σDC [28]. 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 σDC. The addition of GLY to the electrolyte was also attempted to further

improve the σDC. The amorphous structure in the electrolyte complexes can be

enhanced with the inclusion of GLY [37]. 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 processes raise the amorphous phase

in the PEs, subsequently enhancing the electrolyte σDC [28]. The ion conduction is

desirable in the amorphous structure owing to segmental movement of polymer chains

[38, 39]. Moreover, the absence of any XRD peaks associated with pure PVA,

approves the whole dissociation of NH4SCN salt in the PE [38]. The elimination of

hydrogen bonding among the polymer chains causes broadening and weakening in

intensity, which signifies the dominance of the amorphous phase in the PE system

[33].

The addition of GLY and Cu(II)–complex will result in the intensity reduction

of crystalline peaks and vanishes the crystalline peak at 2θ = 20° (see Figure 4). In

13
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 [29]. 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 perceived through the whole range of 2θ degrees.

Obviously, just a hump can be seen from 2θ = 20◦ to 30◦ [29]. 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 crystallinity (Xc) [39], as shown in Figure 4. The large and wide peaks

signify the amorphous peaks, while the narrow, sharp and small peaks indicate the

crystalline peaks. Pure PVA possesses Xc of 41.68, which is noticeably decreased

when GLY is inserted. Thus, the amorphous structure of the systems is enhanced with

the GLY insertion. It is seen in Figure 4 that when GLY is added, crystalline peaks in

PGNC-1 became smaller and less sharp (Figure 4 (c-e)). The addition of GLY with

40 wt.% gives rise to the smaller crystalline peaks, as seen in the XRD pattern of

PGNC-4 (Figure 4(e)). Eq. (6) was used to obtain Xc for pure PVA and doped PVA

and the Xc values are tabulated in Table 1. PGNC-1 system has Xc value of 8.93

while PGNC-4 has the minimum Xc value of 3.54, meaning that the PGNC-4 is the

highest amorphous system in this study [39].

AC
Xc   100% (6)
AT

14
Here, AT and AC refer the total area of the amorphous and crystalline peaks and total

area of the crystalline peaks, respectively, which were accomplished by the

deconvolution method using the OriginPro software. The Gaussian function mode

was employed for the fitting of the XRD spectra.

Figure 4. XRD spectra for (a) pure PVA, (b) PGNC-1, (c) PGNC-2, (d) PGNC-3, and (e) PGNC-4
films.

15
Table 1. The degree of crystallinity from deconvoluted XRD analysis

Electrolyte Degree of crystallinity

(%)

Pure PVA 41.68

PGNC-1 8.93

PGNC-2 7.54

PGNC-3 5.88

PGNC-4 3.54

3.2 FTIR Analysis

The FTIR spectra for pure PVA and PVA:NH4SCN:Cu(II)-complex:GLY are

shown in Figure 5. The following modifications in the spectral features have been

detected after comparing the spectra of pure and doped PVA. C–H rocking of pure

PVA is considered the reason for absorption peak at 838 cm−1 (see Figure 5a,) [33].

In the case of PVA:NH4SCN:Cu(II)-complex:GLY, this peak shifted and its intensity

decreased; whereas, upon the addition of 40 wt.% of GLY it nearly vanished.

It is well-known that in NH4SCN salt–polymer, the charge carrier species are

hydrogen ions (H+) [24]. The new strong and intense peak detected at 2045 cm-1 is

endorsed to aromatic S–C=N stretching of anion of SCN- group of NH4SCN. This

band shifts with considerable intensity reduction upon the addition of the higher GLY

concentration is related to the complexation with PVA functional groups (see Figure

16
5b) [34, 38]. In the ammonium ion NH4+ tetrahedral, since just one of the four protons

(H+) weakly linked to the nitrogen atom; thus, the H+ will transfer to every

coordinating site of PVA. The change in peak place with the emergence of the new

peak in the PVA:NH4SCN:Cu(II)-complex:GLY indicates the complex creation

amongst the PVA and the NH4SCN [34]. The insertion of plasticizer helps further

ions dissociation; therefore, additional ions are offered to create interactions with the

functional groups of PVA [40]. Furthermore, the interaction between PVA functional

groups and Cu(II)–complex was indicated in our previous work [29]. This interaction

or the adsorption of Cu(II)–complex on the functional groups of the PVA is the two

endorsed clarifications for the band intensity reduction [29]. Consequently, since

adsorption causes an increase in the molecular weight, there is a reduction in the

functional groups vibrational intensity [35].

In the meantime, O–H stretching vibration of hydroxyl (OH) groups can be

related with the wide and robust absorption peak at 3340 cm−1 [41]. This band

possesses a high intensity, almost certainly owing to the robust intra and inters kinds

of hydrogen bonding [33]. Additionally, this band shifts and peak intensity drops in

the PVA:NH4SCN:Cu(II)-complex:GLY owing to its complexation with NH4SCN

salt and Cu(II)-complex. The peak at around 1643 cm−1 in the pure PVA is believed to

be originated from the C=O stretching of acetate group [42], in which for the doped

PVA films it is shifted to a smaller wavenumber. C–H asymmetric stretching

vibration is related with a band at 2913 cm−1 [41], which also shifted and reduced

considerably in the case of doped PVA films. Furthermore, the characteristic of –C–

O– stretching vibration in pure PVA is ascribed through the peak at 1076 cm−1 [43],

which is shifted with dropped intensity in the doped films with Cu(II)-complex and

GLY, as shown in Figure 5a.

17
 The C–H bending vibration of CH2 wagging has been recognized as the cause

for the pure PVA absorption peak at 1419 cm−1, while C–H deformation vibration has

been related with the 1317 cm−1 absorption peak in pure PVA (see Figure 5a,) [42]. It

is therefore clear that the PVA:NH4SCN:Cu(II)-complex:GLY samples were related

with shifting of these two peaks and a considerable reduction in the intensity of these

peaks. These modifications in the FTIR spectra are strong evidences for the

interaction of PVA functional groups with the electrolyte components (see Figure 5a,

b).

(b) C=O strtching (a) C-H rocking

C-H stretching band band
C-H bending -C-O- band
O-H band S–C=N stretching

(v)
Transmittance (a.u)%

(v)

Transmittance (a.u)%
(iv) (iv)

(iii) (iii)

(ii)
(ii)
(i)

(i)
C-H deformation
4000 3700 3400 3100 2800 2500 2200 1900 1850 1650 1450 1250 1050 850 650 450
-1
Wavenumber (cm ) Wavenumber (cm )
-1

Figure 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 cm−1 to 1900 cm−1, and (b) 1900 cm−1 to 4000 cm−1.

3.3 Morphological Study

Figure 6a(i-iv) illustrates surface morphology of all the studied films through

FESEM images. It is recognized that the surface morphology of the PE films is the

18
key properties to recognize their behavior [44]. The images were obtained at

500× magnification. The small grey lumps can be seen on the surface of the CPE

films (see Figure 6a(i)). These lumps were attributed to the protrude salts. It is

evident from the images that the grey lumps are disappeared as the GLY

concentration was increased from 20 to 40 wt.%. The CPE has a smooth and uniform

surface morphology without existing a phase separation as shown in Figure 6a(ii-iv).

It is well documented that smooth morphology appearance is related to the amorphous

phase of the PE system [45]. The smooth surface electrolytes can assist conducting

ionic species to pass more easily, and therefore increases the value of σDC [45].

Likewise, the CPE samples with uniform surface in Figure 6a(ii-iv) indicates the fine

dispersion of Cu(II)-complex. The small white spots appearing on the CPE films

surface are attributed to Cu(II)-complex.

This was though, certified to be different in previous works, while extra

agglomerated particles on the surface of the CPE films appeared as excessive fillers

was included in the polymers. For examples, Hamsan et al. [46] determined the σDC

decrement as more GLY was inserted. It has been explained that this is ascribed to the

rearrangement of self-linkages of plasticizer producing recrystallization of salt which

causes a decrease in σDC [47]. Hence, polymer capability is restricted to accommodate

extra salts, which in turn caused recrystallization of salt [48]. Lim et al. [1] have also

connected the surface morphology of CPEs to the σDC. In their work, a fall in σDC

upon addition of 10 wt.% TiO2 has been shown for PVA:LiClO4:TiO2 electrolyte

systems. They proposed that this observation is due to the agglomeration of TiO2.

They related this to the fact that, the CPE surface morphology possesses great level of

rigidity owing to the addition of 10 wt.% TiO2. Thus, these agglomerations could

block conducting pathways for ionic movements. Large rigidity in the back bone of

19
polymer also decreases the ion mobility. Consequently, the σDC is reduced with the

blocking impact and ion transportation is limited.

It is believed that so as to accomplish high σDC, the surface has to be smooth

uniform. In other words, it is linked to the film amorphous structure [49]. The

addition of Cu(II)-complex improved the amorphous phase further as shown in our

previous work [29]. In fact, the interaction between the PVA and electrolyte’s

components is evinced by the smooth uniform surface morphology of the CPE

samples (see Figure 6a(i-iv)).

In this study, the outcomes display that there is an innovation of the PE

preparation as a novel and simple technique to get a great σDC and high performing

EDLC. The FESEM images are in good agreement with the XRD and FTIR results.

From the XRD and FTIR routes, the interaction among the PVA and electrolyte’s

components were validated. It is indicated that the CPE surface morphology is

observed to be nearly smooth and uniform without having obvious protruded salts at

high GLY concentration. From these outcomes, the fabricated CPE was well-defined

with amorphous behavior even at the maximum GLY amount. The role of GYL

content on increasing free ionic species in the prepared samples is schematically

illustrated in Figure 6b.

20
(i) (ii)

Sample ( ( Sample ( (
(F) (F) (F) (F)

(iv) (iii)

Sample Sample
( (( (
(F) (F) (F) (F)

(a)

Figure

6. (a)

Field

emissio

scanni

ng

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.

(b)
21
3.5 Impedance Analysis

The electrochemical and ion transference behaviors of ionic materials, for

example electrodes and PEs, can be efficiently examined by the use of

electrochemical impedance spectroscopy (EIS) [50, 51]. In this work, EIS was used to

analyze the impedance plots for the CPE films (see Figure 7(a-d)). For PGNC-1

system in Figure 7a, a semicircle at high frequency region is resulted from the CPEs

bulk effect, and a tail at low frequencies can be noted. The tail at the low frequencies

happens because of the creation of the EDLC through the free charges buildup at the

electrode and electrolyte interface [52]. The spike or tail was only displayed by the

other samples (see Figure 7(b-d)).

The electrical equivalent circuit (EEC) method is used as a straightforward

way for the EIS examination, which provides the entire image of electrolyte system

[53]. The Nyquist plot for the systems was deduced in terms of the EEC. It comprises

bulk resistance (Rb) for the carriers in the electrolyte systems and two constant phase

elements (CPE) as seen in the insert of Figure 7. The region of high frequencies

displays the connection of Rb and constant phase element in parallel, while the region

of low frequencies indicates only constant phase element, meaning that the formed

EDLC between electrode and electrolyte. The constant phase elements term is more

usually employed in EEC rather than ideal capacitor in the real system.

The impedance of ZCPE can be written as [46,54]:

1   p   p 
Z CPE  p 
cos   i sin   (7)
C   2   2 

Where C stands for the constant phase element capacitance, ω refers the angular

frequency and p is linked to the departure of the EIS plots from the vertical axis. Here,

22
the real (Zr) and imaginary (Zi) parts of complex impedance (Z*) correlated with the

EEC (insert of Figure 7a) are indicated as [54]:

 p   p 
RbC1 p1 cos 1   Rb cos 2 
Z r  Rs   2    2  (8)
 p  C2 p 2
2 RbC1 p1 cos 1   Rb C1  2 p1  1
2 2

 2 

 p   p 
RbC1 p1 sin  1  sin  2 
Zi   2    p2 
2 (9)
p1  p  C2
2 RbC1 cos 1   Rb C1  2 P1  1
2 2

 2 

Where C1 refers the bulk constant phase element capacitance and C2 refers the

constant phase element capacitance at the interface of electrode and electrolyte.

Here, the Zr and Zi parts of Z* associated with the EEC (inset of Figure 7b-d) are

expressed as [54]:

 p 
cos 2  (10)
Z r  Rs   2 
C2 p 2

 p 
sin  2  (11)
2
Zi   p 2 
C2

Table 2 outlines the fitting parameters of the EEC. The Rb is obtained by the

interception between the real axis and the spike. It is obvious that upon the addition of

the GLY, the semicircle at the region of high frequencies were absent (see Figure 7b-

d) due to the complete transport of ions toward the electrodes. The Rb is dropped as

the GLY amount increases to 40 wt% because of the increase in mobility of charge

species, ensuring the rise in the σDC of ions. The increase in σDC with the GLY amount

is consistent with the FESEM results (see Figure 6). The addition of Cu(II)–complex

23
to the PE significantly promoted the amorphous nature that caused to increase the σDC

and improve the EDLC performing. Rangasamy et al., [55] thought that the increase

in the amorphous phase of the PE increases the ions mobility by developing more free

volume in the PE system. This leads to an increase in the polymer chains segmental

motion, due to the rise in the polymer chains flexibility. Therefore, the σDC in the PE

can be improved. Liew [56] had developed the CPE based on PAA:LiTFSI with the

insertion of BaTiO3. The author obtained σDC of 5 × 10–4 S cm–1 and used the CPE in

the EDLC cells. This indicates that CPE is a good candidate to be employed as a PE

in the EDLC device. By considering the Rb value and the CPE dimensions, the σDC of

the CPE films can be calculated using the relation below [57],

 1  t 
 dc    ×   (12)
 Rb   A 

Where t denotes the CPE thickness. A refers to the area of the SS electrode. The

values of σDC of the CPE samples are listed in Table 3. Previous reports have

indicated that PEs with high σDC in the range between 10-5- 10-3 S cm-1 can be

employed for use in EDLCs (see Table 4). The σDC value of the synthesized EDLC is

in comparison with previous works using a number of PEs as recorded in Table 4.

The idea of σDC value was supported in the sense that the σDC depends on the charge

number density (ni) as well as ionic mobility (µi), as follows [58],

 dc   ni qi i (13)
i

Here qi stands for the charge of the species (1.6 × 10−19 C). There was an increase in

σDC when ni and µi inside the system of PE increases, as it is apparent from Eq. (13).

The Table 3 data as well as EIS spectra in Figure 7 obviously indicate that having

more GLY concentration will give rise to the value of σDC. GLY decreases the

24
attraction force between the cations and anions of the salt [27, 28]. Thus, a greater

number of ammonium ions (ni) is offered by NH4SCN to the polymer.

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

Table 3. Achieved σDC of the PVA:NH4SCN:Cu(II)-complex:GLY system at room temperature.

Composition (PVA wt.%:NH4SCN

Designation Rb (Ohm) σDC (S cm-1)
wt.%:Cu(II)–complex mL:GLY wt.%:)
2.28 × 104
PGNC-1 50:50:10:10 5.23 × 10-7
50
PGNC-2 50:50:10:20 3.24 × 10-4
12
PGNC-3 50:50:10:30 1.46 × 10-3
11
PGNC-4 50:50:10:40 2.25 × 10-3

25
 50 20
(a) 18
(b) Experimental
45 Experimental Fitting
40
Rb Fitting 16
Rs
Zi (Ohm) x 10 3

35 14

Zi (Ohm) x 10 2
30 12 Rs CPE
CPE 10
25
CPE
20 8

15 6

10 4

5 2

0 0
0 5 10 15 20 25 30 35 40 45 50 0 2 4 6 8 10 12 14 16 18 20
3 2
Zr (Ohm) x 10 Zr (Ohm) x 10

5.5 4.5
5 (c) (d) Experimental
Experimental 4
Fitting
4.5 Fitting
3.5
4
Zi (Ohm) x 10 2

3 Rs CPE
Zi(Ohm) x 102

3.5
Rs CPE
3 2.5

2.5 2
2
1.5
1.5
1
1
0.5 0.5

0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
2 2
Zr (Ohm) x 10 Zr(Ohm) x 10

Figure 7. Experimental EIS for (a) PGNC-1, (b) PGNC-2, (c) PGNC-3, and (d) PGNC-4
electrolyte films.

Table 4. DC conductivity (σDC) specific capacitance (Cd), energy density (Ed), power density (Pd),
and cycle number of EDLCs using dissimilar PEs at room temperature.

26
 Cycle
Electrolyte composition σDC (S cm-1) Cd (F g−1) Ed (Wh kg−1) Pd (W kg−1) No.
Ref.
PVA:LiClO4:TiO2 1.3 × 10-4 12.5 1.56 198.7 1000 [1]

CMC:KC:NH4NO3 ~10-4 20 - - 10000 [59]

Chitosan:H3PO4:NH4NO3:Al2SiO5 (1.82 ± 0.1) × 10-4 0.2 - - 100 [60]

PAA:LiTFS:BaTiO3 5 × 10–4 34.22 3.32 71.47 20000 [56]

PDMA: MgTf2: Co3O4 9.4 × 10–3 29.48 1.89-2.62 157.7-240.4 8000 [19]

Dextran:NH4Br (1.67 ± 0.36) × 10−6 2.05 - - 100 [61]

PS:MC:NH4NO3:GLY ~10−3 31 3.1 910-385 1000 [46]

PVA:chitosan:NH4NO3:EC 1.6 × 10-3 27.1 - - 100 [62]

MC:NH4Br:GLY (1.89 ± 0.05) × 10−4 - - - - [49]

Chitosan:MC:NH4I 6.65× 10−4 9.97 1.1 578.55 100 [14]

PVA:Naft:BmImBr 2.31× 10−3 16.32 - - 1000 [17]

Chitosan:MC:NH4F 2.96 × 10-3 58.3 7.3 964 100 [18]

PVA:CH3COONH4:BmImBr (9.29 ± 0.01) × 10−3 21.89 1.36 34.66 500 [63]

PVA:dextran:NH4I 2.08 × 10−5 4.2 0.55 64 100 [64]

MC:NH4NO3:PEG 38 3.9 140 100 [65]

MC:dextran:NH4I 1.12 × 10−3 79 8.81 1111.1–170 100 [66]

Cellulose acetate:LiClO4 4.9 × 10−3 90 - - 600 [67]

EMIM-TFSI:PVDF-HFP - 51.8 15.7 1048 3000 [68]

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, NH4NO3 = 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(trifluoromethanesulfoly)
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.

3.6 EDLC Characteristics

3.6.1 Transference Number Measurement (TNM)

TNM is employed to identify the highest carrier species inside the CPE. When 0.2

V is applied, the current commences to decrease until it gets saturation. The current

27
polarization set against time for the maximum conducting CPE (PGNC-4) is

portrayed in Figure 8. The cause for the enormous of the early current value is in

consequence of the part held by the ion and the electron carriers at the early stage.

Figure 8 illustrates that there is a substantial reduction in the current prior it reached

an equilibrium state. Once the CPE was polarized, it is in the equilibrium; whereas,

the maintained current movement is owing to electron species. The cause for that is

the blocking of ions caused by the SS electrodes, which lets only the electron to

transport through it [69]. Eqs. (1) and (2) are employed to evaluate tion and tel values,

which obtaining Ii and Iss values as 279.9 µA and 8.1µA, respectively. The tion and tel

values are established to be 0.971 and 0.029, respectively. It is interesting to note that

the tion is very close to the ideal value of one. Subsequently, it is concluded that ions

have a significant role in the transportation mechanism in the PVA:NH4SCN:Cu(II)–

complex:GLY system.

300
Ii
250
Current (µA)

200

150

100
Iss
50

0
-50 0 50 100 150 200 250 300 350 400 450
Time (s)

Figure 8. Polarization current versus time for the maximum conducting (PGNC-4) CPE film.

3.6.2 Electrochemical Stability Study

28
 The electrochemical stability window (ESW) is an essential characteristic to be

studied [70]. Hence, linear sweep voltammetry (LSV) measurement is led to find the

PE decomposition voltage. The device performance is verified when one is alert of the

ESW of the PE film prior the test of charge-discharge cycles. To avoid causing any

harm to the PE, the decomposition voltage is vital. Figure 9 depicts the LSV plot of

PGNC-4 at 10 mV s−1 with a voltage range of 0 to 2.5 V. There is no obvious change

in the current within the working electrode in the voltage varying from 0 to 2.15 V.

ESW is observed at 2.15 V as the current starts to raise drastically, revealing CPE

decomposition.

This outcome is similar to the work by Liew [56] on PAA:LiTFSI:BaTiO3 CPE

with ESW of 2.3 V. They employed the CPE in an EDLC. Kadir & Arof [62] reported

that the ESW for PVA-chitosan-NH4NO3-EC film is 1.70 V, which is lesser than the

obtained result in our work. The usual ESW for protonic battery use is approximately

1 V [71]. Therefore, the decomposition voltage of PGNC-4 highlights its suitability

for applications in protonic devices. Lim et al. [1] documented that the decomposition

voltage of PVA:LiClO4:TiO2 was found to be 2.4 V and they used the CPE in an

EDLC.

29
 5
Current density (mA/cm )
2

2
Decomposition potential = 2.15 V
1

0
0 0.5 1 1.5 2 2.5 3
Potential (V)

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

3.6.3 Cyclic Voltammetry Study

Cyclic Voltammetry (CV) examination was employed to assess the performance

of EDLC using PGNC-4 CPE. Figure 10 shows the CV plot of EDLC at various scan

rates of 5, 10, 20, 50, and 100 mV s−1. No peak is seen in the CV plot signifying that

no redox reaction happens at the potential range of 0 to 0.9 V. This is verified the

existence of EDLCs [72]. As seen in Figure10, the CV plot shape deviated from a

leaf shape to a nearby shape of a rectangle when the scan rate decreases. High scan

rate causes a departure of the CV plot from rectangular shape that is ascribed to the

internal resistance and carbon porosity; hence, generating a current-voltage

dependence [62]. 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

s−1. The value of CCV increases as the scan rate drops. Ions use the whole vacant sites

through the electrodes where ions have appropriate time for the mechanism of

diffusion at short scan rates, causing in grander value of CCV [73]. The CV shapes

30
acquired in this work is similar to that achieved by Lim et al. [1]. In their study, the

CV at the scan rates of 10, 30, 50, and 100 mV s-1 were created for EDLCs with the

system of PVA:LiClO4:TiO2-based CPE.

20
5 mV/s
10 mV/s
15
20 mV/s
50 mV/s
Current density (mA/cm2)

10 100 mV/s

-5

-10

-15
0 0.2 0.4 0.6 0.8 1
Potential (V)

Figure 10. Cyclic voltammetry (CV) plot of the synthesized EDLC for the largest conducting
(PGNC-4) CPE film.

Table 5. Capacitance values from CV as opposed to scan rates.

Scan rates (mv/s) Capacitance (F/g)

100 64.014
50 100.137
20 123.457
10 132.602
5 134.889

3.7 Galvanostatic charge-discharge analyses

Figure 11a displays the EDLC charge-discharge profile at initial cycles at 0.5 mA

cm−2 current density. The roughly discharge curves with linear slope designates the

31
EDLC capacitive manners [73]. The charge-discharge plot of the EDLC at 0.5 mA

cm-2 for the selected cycles up to 1000th cycles is exposed in Figure 11b, c. It could

be seen that the discharge slope is still almost linear, signifying the presence of

capacitive behavior of the EDLC [73]. Figure 11b,c displays the charge-discharge

performance of the EDLC at specific cycles. At the beginning of charge-discharge

process more ions are available to form double layer thus providing longer discharge

time. As the cycle number increase, the discharge time become shorter, this is due to

recombination of ion to form ion pairs or triplets. The development of ion pairs

reduces the charge double-layer.

1.1

1 (a)
0.9

0.8

0.7
Potential (V)

0.6

0.5

0.4

0.3

0.2

0.1

0
0 1000 2000 3000 4000 5000 6000

Time (s)

32
 1.1000

(b)
0.9500 100th 200th 400th 600th 700th 1000th

0.8000
Voltage (V)

0.6500

0.5000

0.3500
0 400 800 1200 1600 2000 2400
Time (s)

1.0000

0.9000
(c)
100th
0.8000

0.7000 500th
Voltage (V)

0.6000

0.5000 1000th

0.4000

0.3000

0.2000

0.1000

0.0000
0 200 400 600 800
Time (s)

Figure 11. Charge–discharge profiles for the synthesized EDLC at 0.5 mA cm−2 for (a) initial
cycles, (b) selected cycles of 100th, 200th, 400th, 600th, 700th, and 1000th and (c) selected cycles
of 100th, 500th, and 1000th.

The value of Cd is computed by substitution the value of the slope of the discharge

curves in Eq. (4). Figure 12 displays the Cd versus number of cycles. The Cd value

calculated for the 1st cycle is 128.6 F g−1. This value is analogous to the CCV obtained

from CV examination (see Table 5). Therefore, the Cd value accomplished from the

EDLC in this study is responsible. The value of Cd was found to increase and stays

33
constant with the average of 155.32 F g−1 besides the 1st cycle till it finishes 1000

cycles. Though, in previous documents significant decrease of Cd has been discerned

with raising the number of cycles [1, 56]. The achieved Cd in this study is much

higher than those stated in the literature using various PEs (see Table 4).

The development of Cd in the EDLC is ascribed to the higher σDC value of the

CPE due to the influence of the Cu(II)-complex on the enhancement of the amorphous

structure [29], and the addition of GLY plasticizer [46]. As reported by Fan et al. [74],

the development of the amorphous phase is to be beneficial in local chain segmental

motion that can encourage the ions transportation and hence increasing the σDC. Thus,

ions can transfer freely through the PE. Fast ion migration in the CPE also encourages

the adsorption of ions at the interfaces of the electrodes and electrolytes that causes

greater Cd value of EDLC [56].

400

350
Specific capacitance (F/g)

300

250

200

150

100

50

0
0 200 400 600 800 1000
Cycle number

Figure 12. Cd of the synthesized EDLC for 1000 cycles.

The decrease in the voltage throughout the discharging process is caused by the

EDLC internal resistance. The low drop voltage value, Vd, in this study denotes that

less energy is dissipated during the charge-discharge process. The value of Vd is found

by using Eq. (5) and displayed in Figure 13. It can be seen that the increase in the

34
value of Vd is still small throughout 1000 cycles, revealing the high performance of

the fabricated EDLC. The EDLC internal resistance is attributed as equivalent series

resistance (ESR). Therefore, a low ESR is crucial for the EDLC application. As

documented by Arof et al. [75], the ESR in the EDLC is originated from the

resistance of the current collectors, PE, and the space amongst the PE and the current

collector. ESR is determined via Eq. (5), and the values are illustrated in Figure 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 electrodes surface would be

efficient [76]. Kumar & Bhat [77] documented that the increase in Vd among the

cycles of charge-discharge, which creates the increase in ESR is caused by the PE

degradation in the EDLC. Fortunately, the increase in the ESR of the EDLC in the

current work is still small within 1000 cycles. The ESR in the current study is much

lower than the ESR values documented for other EDLC devices [59, 64].

0.9000
0.8000
0.7000
0.6000
Vd (V)

0.5000
0.4000
0.3000
0.2000
0.1000
0.0000
0 200 400 600 800 1000 1200
Cycle number

Figure 13. Vd pattern of the fabricated EDLC for 1000 cycles.

35
 800.00

700.00

600.00
ESR (Ohm)

500.00

400.00

300.00

200.00

100.00

0.00
0 200 400 600 800 1000
Cycle number

Figure 14. ESR pattern of the created EDLC for 1000 cycles.

The energy density (Ed) and power density (Pd) of the EDLC device are achieved

using the following equations [14]:

C sV
Ed  (14)
2

V2
Pd  (15)
4m( ESR)

Where V denotes the used voltage.

From Figure 15, it can be perceived that the value of Ed using Eq. (14) for the 1st

cycle is 14.467 Wh kg−1.The value of Ed exhibits an increase and continues constant

with the average of 17.473 Wh kg−1 within the cycles beyond the 1st cycle up to 1000

cycles. It means that the same energy barrier is subjected by ions species in migration

to the surface of the AC electrodes for the processes of charge-discharge within 1000

cycles. Though, in previous reports noticable decrease in Ed value were noted with

increasing the cycle number [56, 63]. They described that the decrease in the value of

Ed within the cycle number is ascribed to the raise in the ESR that creates the increase

of energy loss through the mechanism of charge-discharge cycles [62, 78]. The

accomplished Ed for the EDLC is sufficiently large compared to that described (3

36
Wh/kg) for PAA:LiTFSI:BaTiO3- based CPE [56]. The obtained Ed in the current

study is of the considerable attention in respect of the Ed value of roughly 1.56 Wh/kg

that found for EDLC of the CPE system of PVA:LiClO4:TiO2 [1]. Fortunately, the

value of Ed (17.473 Wh kg−1) within 1000 cycles in the current work is in the range of

battery energy density and significantly higher than the Ed values reported in the

literature (see Table 4). These results indicate that the Cu(II)-complex as filler has a

great impact on the performance of the EDLC device.

40

35
Energy density (Wh/kg)

30

25

20

15

10

0
0 200 400 600 800 1000

Cycle number

Figure 15. Ed of the synthesized EDLC for 1000 cycles.

The achieved Pd value using Eq. (15) for our study will be seen in Figure 16.

Over charge-discharge within 1000 cycles, the Pd value for the 1st cycle is 4960 W

kg−1 and subjected to a drop up to 500th cycle with the average of 2277 W kg−1 and

then continues constant with the average of 400 W kg−1 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 electrodes and PEs [79]. This tendency of Pd drop is in agreement with the rising

37
ESR tendency. The ESR raise at greater cycles due to the reduction in the mobile ion

concentration and aggregation of ions after the swift processes of charge–discharge

cycles offers smaller Pd at higher cycles [80]. The accomplished Pd for the EDLC cell

is high in comparison to that reported in the literature (see Table 4).

8000

7000
Power density (W/kg)

6000

5000

4000

3000

2000

1000

0
0 200 400 600 800 1000 1200
Cycle number

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

4. Conclusion

PVA:NH4SCN:Cu(II)-complex:GLY -based CPE was efficiently fabricated using the

solution casting process. The addition of Cu(II)-complex and GLY maximized the σDC
up to 2.25×10-3 Scm−1. Outcome from the XRD route displayed that the highest
glycerolized CPE exhibits the most amorphousity. 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 conductivity variation of the CPE sytems. Using the
FTIR route, the interaction amongst PVA and the PE components was confirmed. The
FESEM route revealed that the films surface morphology 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 displayed that the decomposition voltage for
PGNC-4 system is at 2.15 V, suggesting its appropriateness in the EDLC application.
Capacitive manner in the synthesized EDLC was confirmed 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 155.322 F/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 work is in the range of
battery energy density. The low value of ESR indicates that the EDLC has a proper

38
contact among the AC electrodes and the PEs. The EDLC has initial high Pd as
4960.31 W/Kg.

Acknowledgments

The authors appreciatively acknowledge the financial support for this work by the
Ministry of Higher Education & Scientific Research-Kurdish National Research
Council (KNRC).

Conflicts of Interest

The authors declare no conflict of interest.

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