Electrochimica Acta 461 (2023) 142659

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.journals.elsevier.com/electrochimica-acta

Magnesium ion conducting biopolymer blend-based electrolyte for energy

storage application: Electrochemical characteristics
Shujahadeen B. Aziz a, b, **, Mowfaq J. Ahmed c, Omed Gh. Abdullah a, *, Ary R. Murad d,
Samir M. Hamad e, Jihad M. Hadi f
a
Advanced Polymeric Materials Research Laboratory, Department of Physics, College of Science, University of Sulaimani, Qlyasan Street, Sulaymaniyah, Kurdistan
Region 46001, Iraq
b
The Development Center for Research and Training (DCRT), University of Human Development, Sulaymaniyah, Kurdistan Region 46001, Iraq
c
Department of Physics, College of Education, Salahaddin University-Erbil, Kurdistan Region 44001, Iraq
d
Department of Chemistry, College of Sciences, Charmo University, Chamchamal, Sulaymaniyah, Kurdistan Region 46023, Iraq
e
Scientific Research Centre, Soran University, Kawa Street, Soran, Erbil, Kurdistan Region 44008, Iraq
f
Nursing Department, College of Nursing, University of Human Development, Sulaymaniyah, Kurdistan Region 46001, Iraq

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

Keywords: A casting technique was employed to produce plasticized magnesium ion conducting biopolymer blend elec­
Biopolymer blends trolytes. Chitosan (CS) and polyvinyl alcohol (PVA) were used to deliver polymer blends, and 50 wt.% of
Magnesium ions magnesium nitrate (Mg(NO3)2) was incorporated as the source for Mg2+ ions supply. The CS:PVA:Mg(NO3)2
Dielectric relaxation
system was subjected to different concentrations of glycerol plasticizer to improve its ion conductivity. To assess
Electrical modulus
LSV
their suitability as energy storage materials, the electrochemical characteristics of the fabricated films were
CV study examined employing broad methodologies. Distinguished improvement in dielectric constant was observed upon
increasing plasticizer concentration. The appearance of relaxation peak in tanδ-M’’ spectra and their asymmetric
shape reveals the non-Debye relaxation process. The biopolymer blend electrolyte, with a plasticizer content of
55 wt.%, exhibited the highest DC conductivity, measuring 7.34 × 10− 5 S.cm− 1. In terms of potential stability,
linear sweep voltammetry (LSV) analysis revealed a value of 2.34 V for this particular electrolyte. A non-Faradaic
(capacitive) response to cyclic voltammetry (CV) is displayed, and there is no redox peak. The selected scan rate
influenced the shape of the CV curves. When scan rates of 20 mV/s and 100 mV/s were employed, specific
capacitance values of 5.41 and 16.46 F/g were determined. The stability of an electrochemical double-layer
capacitor, which serves as an energy storage device, was evaluated by employing a charging-discharging tech­
nique and the electrode separator made of the most conducting sample. The results show promise for the po­
tential application of the current plasticized magnesium ion-conducting biopolymer blend electrolyte in energy
storage devices.

1. Introduction interactions between the intermolecular of the mixed polymers, this

In recent decades, solid polymer electrolytes (SPEs) have become
increasingly important in electrochemical devices, particularly elec­
trical double-layer capacitors (EDLCs). Liquid electrolytes have limita­
tions, which is why SPEs have been extensively researched as a possible
alternative. SPEs have many benefits, such as being safer, having a
longer shelf life, and being easy to make [1–3]. Combining different
polymers is known to enhance mechanical strength, thermal stability,
and ionic conductivity, making it a desirable approach. Due to the
technique will make the matrix less crystalline, increasing the site’s
availability for ions to hop across the SPEs [4].
The creation of SPEs, on the other hand, relies heavily on natural
biopolymers because of their unique qualities, such as their capacity for
biodegradation and compliance with green chemistry requirements [5,
6]. Biodegradable polymers, such as chitosan (CS) and polyvinyl alcohol
(PVA), have been extensively studied for their potential use in energy
storage devices [7]. CS is a semicrystalline polysaccharide that contains
randomly arranged D-glucuronic acid and N-acetyl-D-glucosamine units.

* Corresponding author.
** Co-corresponding author.
E-mail addresses: shujahadeenaziz@gmail.com (S.B. Aziz), omed.abdullah@univsul.edu.iq (O.Gh. Abdullah).

https://doi.org/10.1016/j.electacta.2023.142659
Received 23 April 2023; Received in revised form 14 May 2023; Accepted 25 May 2023
Available online 26 May 2023
0013-4686/© 2023 Elsevier Ltd. All rights reserved.
S.B. Aziz et al.
These units are linked by β-(1,4) glycosidic linkages. Chitin is subjected
to an acidic or alkaline deacetylation process to produce CS polymer.
High biodegradability, biocompatibility, and non-toxicity are charac­
teristics of CS, which can be produced using simple, low-cost processes
[8]. Polyvinyl alcohol (PVA) follows a similar pattern; it is a cheap,
biodegradable polymer made up of vinyl alcohol groups, which include
polar oxygen atoms. SPE complexes may be created because these atoms
facilitate complexation with salt cations [9,10]. In addition to its
extraordinary film-forming ability [11], PVA is known for its high
dielectric strength, good chemical stability, good transparency, high
charge-storage capacity, and electrical properties that change depend­
ing on the dopant. Several SPE systems have made use of host matrices
made of a combination of CS and PVA [12–14].
Inadequate surface interactions with electrodes and low ionic con­
ductivity at room temperature are two major barriers to SPE practical
implementation [15]. As ionic conductivity is crucial for electro­
chemical energy storage devices, several salts have been added to the
electrolyte to boost it [7]. Currently, due to the environmental impact of
lithium-salts, Na+, Mg2+, H+, and NH+ 4 ions are thought of as Li ions’
+
substitutes in SPEs [16–18]. For instance, Polu and Kumar [19] observed
that the conductivity of PVA at ambient temperature increased from 5.9
× 10− 9 S.cm− 1 to 7.36 × 10− 7 S.cm− 1 at 30 wt% loading as the Mg
(NO3)2 salt concentration increased. A different study examined how
mixing PVA with polyvinyl pyrrolidone (PVP) affected the ionic con­
ductivity of SPEs made of PVA/PVP/Mg(NO3)2. It demonstrated an in­
crease in maximal ionic conductivity up to 3.78 × 10− 5 S.cm− 1 for the
same loading rate (30 wt.%) of Mg(NO3)2 salt [20].
The ionic conductivity of SPEs can be further increased by incorpo­
rating suitable plasticizers [21]. Glycerol is widely employed as a plas­
ticizer to enhance the conductivity of SPEs primarily due to the
abundance of hydroxyl groups (OH) present in its structure [22]. In their
recent study, Asnawi et al. [23] examined the impact of various glycerol
concentrations as a plasticizer on the electrical properties of
chitosan/dextran-NaTf SPE. The findings revealed that the addition of
plasticizer had a substantial positive effect on both ionic conductivity
and the potential stability of the electrolyte system.
A potential substitute for traditional batteries is the EDLCs, which
operate on electrostatic phenomena at the interface between the elec­
trode surface and electrolyte [7]. Researchers have discovered that
compared to other storage systems, EDLC has fairly strong endurance, a
high-power density, and a longer lifespan [24,25]. An intriguing aspect
of this technology is its low cost and straightforward manufacturing
procedure. Carbon materials, particularly carbon nanotubes, graphene,
porous carbon, and activated carbon, have been recognized as suitable
for producing EDLCs due to their high energy storage and economical
nature [26,27]. Furthermore, in the energy storage process of EDLC
devices, a double layer is formed at the interface due to the accumula­
tion of ions. It is important to note that this process is fundamentally
non-Faradaic, meaning it does not involve any chemical reactions or
charge transfer [28,29]. The surfaces of the electrodes and electrolytes,
in other words, do not experience any electron transport. Only a charge
accumulation exists in its place.
In the current study, biopolymer blends electrolytes capable of
transporting Mg-ions was created by combining a CS/PVA blend with
Mg(NO3)2 salt. The study focused on investigating the effect of glycerol
plasticizers in improving the electrochemical parameters of the system.
The ionic conductivity of plasticized SPEs produced at ambient tem­
perature was analyzed using electrical impedance spectroscopy. The
EDLCs were fabricated using the sample exhibiting the highest ionic
conductivity, and their performance was evaluated by utilizing LSV
(Linear Sweep Voltammetry) and CV (Cyclic Voltammetry) techniques.
2
Electrochimica Acta 461 (2023) 142659
2. Experimental
2.1. Materials and sample preparation
Chitosan (CS), polyvinyl alcohol (PVA), and magnesium nitrate (Mg
(NO3)2) are all needed to make the CS:PVA:Mg(NO3)2 host matrix. CS
has a molecular weight of 310,000–375,00 g/mol, whereas PVA has a
molecular weight of 35,000 g/mol; additionally, magnesium nitrate (Mg
(NO3)2) serves as a source of Mg-ions in the mixture. The solution-cast
method required the use of acetic acid (CH3COOH) and double-
distilled water as a solvent for polymeric materials. The compounds
used were acquired from Sigma-Aldrich and used as-is, without any
purification.
To make the biopolymer blend host matrix, 1 g of CS was dispersed in
60 mL of the 1% acetic acid solution using a magnetic agitator for
several hours at room temperature. In the meantime, 1 g of PVA was
completely dissolved by being stirred continuously for many hours at
80 ◦ C while being dissolved in 60 mL of double-distilled water. The two
polymer solutions were continuously stirred at room temperature after
the PVA solution had cooled to room temperature to create a homoge­
nous viscous solution. Following this, 50 wt.% of Mg(NO3)2 salt con­
centration was added to the CS:PVA blended solutions while stirring to
create a homogenous mixture. Subsequently, different glycerol con­
centrations ranging from 11 to 55 wt.% were added to each solution in
increments of 11 wt.%. Each prepared solution was then put into a clean,
labeled Petri dish, allowing the solvent to evaporate at room tempera­
ture to form the film gently. Lastly, the CS:PVA:Mg(NO3)2-glycerol
biopolymer blend-based electrolyte systems with glycerol incorporation
of 11, 22, 33, 44, and 55 wt.%, respectively, were coded as
CSPVMGNT1, CSPVMGNT2, CSPVMGNT3, CSPVMGNT4, and
CSPVMGNT5.
2.2. Fabrication of the EDLC device
For an EDLC, 6.25 percent carbon black (CB) and 81.25 percent
activated carbon (AC) are blended for 20 min at 500 rpm in a planetary
ball mill. The resultant powder combination (AC:CB) is then dissolved in
15 mL of N-methy-2-pyrrolidone (NMP) with 12.5% polyvinylidene
fluoride (PVdF) binder until the solution turns thick and black. Next, the
doctor blading technique is used to apply the black solution to the 0.25
mm thick aluminum foil. After that, the coated aluminum foils undergo
a quick drying process in an oven set to 60 ◦ C. After the electrodes have
dried, a disk is formed that has a geometric area of 2.01 cm2. The EDLC
assembly shown in Fig. 1 has the AC electrode, highest conducting
electrolyte, and AC electrode arranged in that order. The cell was
encapsulated in this design within a CR2032 coin that was placed in a
Teflon case.
2.3. Sample characterization
2.3.1. Electrical study
Resistance vs. reactance for the synthesized SPEs samples was
measured for the free-standing CSPVMGNT electrolyte using the Hioki
3531 LCR meter with an impedance analyzer over a wide frequency
range of (5 − 5 × 106 Hz). The films were disk-shaped, with a diameter
of around 2 cm. They were compressed between two cylinders of
stainless steel blocking electrodes to provide good, tight contact.
2.3.2. LSV study
Linear sweep voltammetry (LSV) was used to look at the electrolyte
potential window of the produced films. The Digi-IVY DY2300 poten­
tiostat, operating at a scan rate of 20 mV/s, was used to take the LSV
readings. The 0–3.5 V potential range was chosen since it is optimal at
ambient temperature.
S.B. Aziz et al. Electrochimica Acta 461 (2023) 142659

Fig. 1. Schematic of the EDLC arrangement and electrode formation.

2.3.3. CV study polarization effects in biopolymer blend electrolyte systems. The

CV is a preliminary test method, was utilized to evaluate the pro­
duced EDLC’s energy storage mechanism at ambient temperature. A
Digi-IVY DY2300 potentiostat has been employed for this investigation,
with varying sweep rates of 20, 50, and 100 mV/s and a potential sweep
of 0 to 1 V.
3. Results and discussion
3.1. Dielectric properties
The study aimed to investigate the behavior of ion conduction and
dielectric characteristics of the CSPVMGNT were examined to under­
stand the energy storage and wasted energy from the mobility of ions.
The dielectric constant helped determine the polarity of the polymers
and the energy stored in each cycle, while the dielectric loss described
the energy wasted due to ion mobility [30,31].
In the study, the dielectric properties of a material were analyzed in
different conditions, such as at room temperature and at different fre­
quencies. Figs. 2 and 3 show the values for the dielectric constant and
dielectric loss, which were measured. At low frequencies, it was seen
that the dielectric parameters were high, which meant that the elec­
trodes were becoming polarized because of space-charge effects. The

Fig. 2. The change of dielectric constant with respect to frequency for biopolymer blend electrolyte systems of CSPVMGNT at room temperature.

3
S.B. Aziz et al. Electrochimica Acta 461 (2023) 142659

Fig. 3. The change of dielectric loss with respect to frequency for biopolymer blend electrolyte systems of CSPVMGNT at room temperature.

size of the polarization area was essential for estimating the mobility and
effective ion concentration, which are crucial factors in the development
of EDLC devices with high capacitance [32–34].
The results also showed that at low frequencies, the dielectric con­
stant and dielectric loss values were higher, which was attributed to
interfacial polarization. This phenomenon was not dependent on the
bulk characteristics of the electrolyte but rather on the increase in the
charge carrier concentration at the interface. At higher frequencies, the
dielectric constant and dielectric loss values decreased non-linearly and
eventually reached a steady-state [35,36].

Fig. 4. The change of (tan δ) with respect to frequency for biopolymer blend electrolyte systems of CSPVMGNT at room temperature.

4
S.B. Aziz et al. Electrochimica Acta 461 (2023) 142659

The dielectric constant and dielectric loss values were expected to
plateau at lower frequencies and exhibit power law dispersion at higher
frequencies. This was in line with the theoretical analysis of electrode
polarization by Klein et al. [35]. These behaviors are well depicted in the
spectra of ε’ and ε" for the current electrolyte system. Furthermore,
Figs. 2 and 3 show an increase in the ε’ and ε" values as a proportion of
the plasticizer content in the system, which is attributed to increase in
charge carrier concentration [37]. For the current plasticized
CS-PVA-Mg(NO3)2 biopolymer blend electrolyte systems, particularly
the CSPVMGNT5 sample, there is a substantial increase in the ε’ because
of the sample’s high ionic conductivity in the low-frequency range. On
the other hand, a larger dielectric constant of SPE connects with a
greater capacity of the matrix to dissolve salts [38,39].
In the current CSPVMGNT biopolymer blend electrolyte systems, the
loss tangent (tan δ) was examined in order to find the relaxation
behavior. Fig. 4 shows the change of tangent loss (tan δ) for the
CSPVMGNT films against the applied frequency at the surrounding
temperature. The tan δ clearly showed an increasing tendency with
increasing frequency, and it attained its maximum value at a specific
frequency before declining steadily beyond that point.
This is because the active (ohmic) component rises faster than the
reactive (capacitive) component at low frequencies. At higher fre­
quencies, however, the ohmic component almost completely loses its
frequency dependence, and the capacitive component rises in direct
proportion to frequency [40]. This trend of change has previously been
observed in several SPE systems [14]. It can be shown that the system
has a non-Debye type dielectric relaxation process since there is a broad
single peak at the mid-frequency of tan δ [41,42]. The peak position of
tan δ was used to calculate relaxation time for all plasticized SPEs and
was found to be 1.32 × 10− 3, 7.58 × 10− 4, 6.06 × 10− 5, 9.23 × 10− 6,
and 1.63 × 10− 6 s for CSPVMGNT1, CSPVMGNT2, CSPVMGNT3,
CSPVMGNT4, and CSPVMGNT5, respectively. As a result, the emer­
gence of tan peaks and the corresponding shift in their position with
increasing plasticizer content provide evidence for the dielectric relax­
ation phenomenon [43]. SPE films become polarized when an external
electric field is applied via microscopic rearrangements of ions, elec­
trons, atoms, and molecules to line up with the external field. Relaxation
times of SPEs are influenced by a variety of factors, including the size of
the polymer mobile segments [44]. According to earlier studies, the
amorphous phase increases and more salts dissolve when polymers are
blended together to form a matrix of SPEs [36]. This resulted in a chain
increase and polymer segmental motion [45]. Increased polymer chain
segmental mobility has been shown to reduce relaxing time, which ac­
celerates the ion transportation process. When glycerol plasticizer is
added, the ε’ increases, and the relaxation peak in the tan δ plot shifts
toward higher frequencies, indicating a shorter relaxation time. Because
of a rise in segmental motion within the system, which causes an in­
crease in the ions’ mobility, therefore, the ion conductivity increases
[46].
3.2. Electric modulus analysis
In order to better understand the conductivity relaxation processes
that take place in ion-conducting electrolytes, the electric modulus
formalism is an efficient method [47]. The complex electric modulus
(M*), the opposite of the complex electric permittivity, can be used to
study how ion relaxation affects the electrical properties of polymers
(M*=1/ε*). This method has the advantage of suppressing the electrode
polarization effects brought on by charge accumulation in the interfacial
region [48,49].
Figs. 5 and 6 display the real (M’) and imaginary (M") plots of the
electric modulus with respect to frequency. It is clear that M’ and M" rise
as the frequency scans toward relatively high values, suppressing elec­
trode polarization processes at low frequencies.
The fact that M’ approaches maximal saturation as the dielectric
constant decreases at a particular frequency is very interesting [50].
Unlike the ε" spectra (Fig. 3), the M" spectra have discrete peaks that are
brought on by conductivity relaxation (see Fig. 6).
Recently, the research work has highlighted how the DC conductivity
(ohmic resistance) affects the ε" parameter in spectra but does not result

Fig. 5. Real portion of electric modulus (M’) with respect to frequency for plasticized CS:PVA:Mg(NO3)2 biopolymer blend electrolyte systems at ambient
temperature.

5
S.B. Aziz et al.
Fig. 6. Imaginary portion of electric modulus (M’) with respect to frequency for plasticized CS:PVA:Mg(NO3)2 biopolymer blend electrolyte systems at ambient
temperature.
in loss peaks to occur [48]. Lower M’ values, as a result of a higher
plasticizer content, show that the presence of glycerol enhances the real
part of the dielectric permittivity (ε’). Notably, the more intense relax­
ation peak, which appears to depend on glycerol concentration, occurs
in the middle-frequency range of M". As the glycerol concentration rises,
the loss maxima fall monotonically. With an increase in frequency, the
peak frequency indicates a shift from long-range to short-range mobility,
and the peak value in M" reflects the actual dielectric spin relaxation
process of the components. This shows that when plasticizer concen­
tration rises, relaxation time reduces.
3.3. Conductivity analysis
The dependence of the applied frequency on AC conductivity (σac)
for all plasticized CS:PVA:Mg(NO3)2 biopolymer blend electrolyte
samples are displayed in Fig. 7 at room temperature. Three separate
sectors, comprising the low, middle, and high-frequency regions, can be
identified for the high salt concentration samples (CSPVMGNT3,
CSPVMGNT4, and CSPVMGNT5). The standard electrode polarization
effect manifests at low frequencies. It appears as a plateau region cor­
responding to the bulk DC conductivity and, accurately linked with
compound concentration, is known as the low-frequency dispersion
zone. A noteworthy observation is that as the salt concentration in­
creases, the relaxation process shifts and results in the produce of AC
conductivity in the high-frequency range [14]. Ions are more likely to
relocate to a more favorable site and then return to their original posi­
tion at higher frequencies [51]. The higher conductivity at higher fre­
quencies, which denotes dispersion, is explained by this high
probability. Charge carrier confinement over the entire sample provides
the AC conductivity phenomena [52]. The universal power law of
Jonscher [53] says that the huge dispersion zone of AC conductivity at
high frequency depends on frequency as a power law with an exponent
that is close to one.
The AC conductivity data presented in Fig. 7 were used to estimate
the DC conductivity value of each plasticized biopolymer electrolyte and
found to be 9.17 × 10− 9, 1.69 × 10− 7, 2.98 × 10− 6, 1.57 × 10− 5, and
6
Electrochimica Acta 461 (2023) 142659
7.34 × 10− 5 S.cm− 1, for CSPVMGNT1, CSPVMGNT2, CSPVMGNT3,
CSPVMGNT4, and CSPVMGNT5, respectively. It is clear that the DC
conductivity increases with increased plasticizer concentration while
the relaxation time decreases (Fig. 4). In other words, the variation in DC
conductivity is opposite to the interpretation in relaxation time. As more
plasticizer is added, the amorphous area expands, resulting in weak and
loose molecular packing. As a result, the polymer chain is easier to orient
at high glycerol content, resulting in a shorter relaxation period [40].
3.4. Linear sweep voltammetry (LSV) study
Potential stability is the most crucial requirement for employing
polymer electrolytes in energy devices. In other words, an electrolyte
must possess great electrochemical stability in order to be used in energy
devices. This study aimed to use the linear sweep voltammetry method
to figure out the electrochemical stability window of the most conduc­
tive SPE film (CSPVMGNT5). This was done to make sure that the
electrolyte could handle the rapid cycle of charging and discharging in
the EDLC.
The results showed the current-potential curve of the CSPVMGNT5
sample up to a potential window of 3.5 V, which is depicted in Fig. 8. It
was observed that there were no current fluctuations up to a potential of
2.34 V, indicating that the electrolyte was stable. However, there was a
sharp rise in the current value beyond this point, indicating that
oxidation had begun. Thus, CSPVMGNT5 has a decomposition voltage of
2.34 V. Similar results on the potential stability window for various
polymer electrolytes have already been published by a number of re­
searchers. For instance, the electrochemical stability of 1.9 V for a
polymer (ether urethane) based magnesium ion SPE was reported by Jo
et al. [54]. Kiruthika and colleagues [55] examined a pectin-magnesium
chloride (MgCl2) electrolyte system. They found that the most conduc­
tive sample had an electrochemical stability of 2.05 V. Meanwhile,
Hamsan, and colleagues [56,57] reported potential stability windows of
2.4 V for the CS:Mg(CH3COO)2:glycerol electrolyte system and 1.83 V
for the CS:MgCl2:glycerol system. Both electrolyte systems were used to
create an EDLC device. For an EDLC device with a potential window of
S.B. Aziz et al. Electrochimica Acta 461 (2023) 142659

Fig. 7. AC conductivity spectra for all plasticized CS:PVA:Mg(NO3)2 biopolymer blend electrolyte systems at ambient temperature.

only 1 Volt, a CSPVMGNT5 film with a sufficiently high breakdown
voltage is the most appropriate choice [22,58]. This sample’s adequate
stability makes it suitable for use in producing EDLC and energy storage
devices.
3.5. Cyclic voltammetry (CV) analysis
Measurement of cyclic voltammetry (CV) was also a part of the EDLC
characterization process. Fig. 9 illustrates the impact of various scan
rates on the CV form of the created EDLC. Fig. 10 demonstrates the EDLC

7
S.B. Aziz et al. Electrochimica Acta 461 (2023) 142659

Fig. 8. Linear Sweep Voltammetry curve for CSPVMGNT5.

Fig. 9. CV plot of the present built EDLC.

diagram for the CSPVMGNT5. CV (Cyclic Voltammetry) response for a capacitor. However, when
The form of the CV plot has a leaf-like appearance for all scan rate dealing with a real capacitor, several factors need to be considered, such
levels. The rectangular shape is widely regarded as offering the optimal as its internal resistance and the transparency of the electrode [59].

8
S.B. Aziz et al.
Fig. 10. The EDLC diagram for the CSPVMGNT5.
These two characteristics directly impact the current-voltage relation­
ship across the EDLC [60]. The electrical energy storage mechanism is a
non-Faradaic process, and the observed CV response of the current EDLC
showed no reduction/oxidation peak throughout its whole potential
range. Ions participate in adsorption and desorption procedures on the
surfaces of negative and positive electrodes, respectively, in the
non-Faradaic process instead of intercalation and deintercalation oper­
ations [61].
The following formula was applied to the CV graph in order to derive
the value of the specific capacitance [5]:
∫ V2
V
IV dV
CS = 1
2mS ΔV
∫V2
where IV dV is the region of the CV profile as determined by Origin
V1
9.0 software. m represents the mass of electrodes composed of active
materials, S denotes the scan rate, and V represents the potential win­
dow (ΔV = 1 V). Table 1 shows that a high CS can be achieved with lower
scan rates. When scan rates are low, a stable double-layer charge is
formed by the ions located at the interface between the electrode sur­
faces and the electrolyte membrane, producing a high capacitance. At a
slow scan rate of 20 mV/s, the cyclic voltammetry (CV) plot shows a
plateau that is almost perfect; this means that free ions move at a fairly
constant speed. Consequently, generate ion accumulation at the
electrode-electrolyte contact surfaces by using very little ohmic resis­
tance. It is important to note that at high scan rates, a thin diffuse layer
forms between the electrode surface and electrolyte film. This leads to
faster ionic conduction, which in turn prevents the necessary polariza­
tion process from taking place [62].
In comparison to other investigations that utilized different magne­
sium salts as Mg2+ ion suppliers, such as magnesium chloride (MgCl2)
and magnesium acetate [Mg(CH3COO)2], the CS values of the EDLC are
regarded as decent in this work. As compared to MgCl2 (2582.13 kJ/
mol) and Mg(CH3COO)2 (2627.64 kJ/mol), the magnesium salt utilized
in this work, MgNO3, has a lower lattice energy of 2429.51 kJ/mol [57].
It is commonly known that salts with lower lattice energies tend to
dissociate more readily than salts with higher lattice energies. Ion pair
recombination can potentially be avoided more often because of the
lower lattice energy value. The capacitance value rises as a consequence
of the abundance of free ions that are generated.
Table 1
The specific capacitance (CS ) calculated from the CV curve at various scan rates.
S (mV/s) A x 10− 3
m(g) x 10− 3
ΔV (V)
100 2.63 2.43 1.0
50 2.44 2.43 1.0
20 1.60 2.43 1.0
Electrochimica Acta 461 (2023) 142659
3.6. Charge-discharge study
The experimental setup involved using a constant current density of
0.2 mA/cm2 to study the charge-discharge pattern of the EDLC, as
shown in Fig. 11.
During the charging process, ionic charges moved from the bulk of
the electrolyte to the surface, forming a double layer with capacitive
characteristics [63]. The EDLC’s capacitive nature was confirmed by the
linear discharge curve observed in Fig. 11. To calculate the specific
capacitance (Cs) and equivalent series resistance (ESR) of the EDLC, the
researchers employed certain equations based on the charge-discharge
response:
i
Cs =
sm
Vdrop
ESR =
i
Wher i, s, m, and Vdrop stand for applied current, discharge part
gradient, active material mass, and drop potential, respectively. As
shown in Fig. 12, the Cs value was initially lower and grew up to the
50th cycle before remaining nearly constant up to the 500th cycle. This
can be attributed to the homogeneity of the electrolyte-electrode area
[64]. The ion polarization stabilization state is a fascinating result that
refers to the constant value of Cs after 100 cycles.
Fig. 13 shows that the expected ESR value would be in the range of
114 to 136 Ω. This value is relatively high, which can be attributed to the
presence of PVdF in the electrode composition. Since PVdF is an insu­
lator, it restricts the flow of carbonic electrons. As shown in Fig. 14, the
energy density (Ed) in the first cycle was found to be 9.5 Wh/kg using
the below formula [65,66]:
Cs V 2
Ed =
2
The Ed increases from 9.5 Wh/kg to 10.6 Wh/kg in the first 50 cycles
and remains stable from the 50th cycle to the 500th cycle. Therefore, it
can be concluded that the energy barrier for ion conduction remains
relatively constant after the 50th cycle. In this study, the Ed value was
measured and compared to other EDLCs that used different materials.
For example, Hina et al. [67] demonstrated an Ed value of 9.82 Wh/kg
for their EDLC, which changed with salt concentration after incorpo­
rating 10% lithium trifluoromethane sulfonate (LiTf) salt in poly
(acrylamide) hydrogel electrolytes. In contrast, the EDLC constructed by
Mazuki et al. [68] achieved an Ed value of only 1.19 Wh/kg for the
CMC-PVA doped NH4Br-based SPE system. The high ionic conductivity
of the current system may be the reason for the high Ed value observed in
this study. Furthermore, by applying the following equation, the ESR
values are utilized to determine the power density (Pd) values [69]:
Pd =
V2
4m(ESR)
Fig. 15 demonstrates that the power density (Pd) of the EDLC reaches
its peak at 905 W/kg during the first cycle but decreases to 752 W/kg by
the 500th cycle. Rapid charging and discharging causes electrolyte
deterioration, which in turn reduces Pd at higher cycle numbers due to
increased resistance and ionic agglomeration [70]. The active material
mass used to make the EDLC has a substantial effect on the values of Pd
(Fig. 15) and Ed (Fig. 14). Low current and light bulk loadings were
found to aid in increasing electrolytic performance [71]. These results
show that biopolymer-based electrolytes, such as synthesized plasticized
CS:PVA:Mg(NO3)2, can be beneficial in energy-storing applications.
Fig. 16 shows the Ed and Pd for electrochemical devices based on the
CS (F/g) Ragone plot. The energy and power levels of electrochemical devices,
such as batteries and fuel cells, are measured and displayed on a Ragone
5.41
10.04 plot. Pd measures how fast the energy can be transmitted, whereas Ed
16.46 measures the quantity of energy held per unit of mass or space. The
9
S.B. Aziz et al. Electrochimica Acta 461 (2023) 142659

Fig. 11. The manufactured EDLC’s charge-discharge curve.

Fig. 12. Specific capacitance (Cs) trend of the manufactured EDLC throughout 500 cycles.

Ragone map contrasts the trade-offs between these two attributes and Ragone plot is a crucial instrument for comprehending the functionality
offers details on how various gadgets perform. It is a useful instrument of electrochemical devices and enhancing their design for real-world
for building and creating new energy storage technologies as it aids in application. The present research demonstrated a useful energy den­
determining which devices are most appropriate for particular uses. The sity value of approximately 10 W/kg, which is adequate and comparable

10
S.B. Aziz et al. Electrochimica Acta 461 (2023) 142659

Fig. 13. Equivalent series resistance (ESR) with respect to cycle number of the manufactured EDLC.

Fig. 14. A plot depicting the energy density of the created EDLC over 500 cycles.

11
S.B. Aziz et al. Electrochimica Acta 461 (2023) 142659

Fig. 15. A plot depicting the power density of the created EDLC over 500 cycles.

Fig. 16. The Ed and Pd for electrochemical devices based on the Ragone plot.

with many previous studies.
This metric indicates that the device has a significant energy storage
capacity relative to its weight, making it well-suited for applications
where weight is a constraint, such as handheld electronic devices and
electric cars. Due to its high energy density, the device can provide
prolonged power, reducing the requirement for frequent recharging or
replacement.
4. Conclusions
Plasticized biopolymer blend electrolytes based on CS:PVA:Mg
(NO3)2 with varying amounts of glycerol were fabricated using a solu­
tion casting method to facilitate the transport of magnesium ions. The
peak appearance for the current compounds displayed a non-Debye type
of relaxation mechanism, according to the dielectric relaxation analysis.
The conductivity was increased to 7.34 × 10− 5 S/cm by the addition of
55 wt.% of glycerol plasticizer. The current electrolyte can be used to
produce an EDLC energy storage device and has a potential stability
value of 2.34 V, which is suitable for the most effective biopolymer
blend electrolyte. Additionally, it has been proven that the current
electrolyte system displays a noteworthy capacitance characteristic. It is
also explained how the correlation between scan rate and specific
capacitance evolves over time, specific capacitance increases at lower
scan speeds but decreases at higher ones. The current biopolymer blend
electrolyte is considered a promising alternative for energy storage de­
vices due to its notable advantages in terms of safety and affordability.

12
S.B. Aziz et al.
Data availability
The authors confirm that the data supporting the findings of this
study are available within the article.
CRediT authorship contribution statement
Shujahadeen B. Aziz: Investigation, Conceptualization, Formal
analysis, Writing – review & editing. Mowfaq J. Ahmed: Validation,
Visualization, Writing – review & editing. Omed Gh. Abdullah: Writing
– original draft, Conceptualization, Formal analysis, Writing – review &
editing. Ary R. Murad: Investigation, Writing – review & editing. Samir
M. Hamad: Visualization, Writing – review & editing. Jihad M. Hadi:
Investigation, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Funding
This research received no external funding.
Acknowledgments
The authors gratefully acknowledge the support and facility for this
study from the Ministry of Higher Education and Scientific Research,
Kurdistan Regional Government, Department of Physics, College of
Science, University of Sulaimani.
References
[1] M.H. Buraidah, S. Shah, L.P. Teo, F.I. Chowdhury, M.A. Careem, I. Albinsson, B.
E. Mellander, A.K. Arof, High efficient dye sensitized solar cells using
phthaloylchitosan based gel polymer electrolytes, Electrochim. Acta 245 (2017)
846–853.
[2] N.H. Zainol, Z. Osman, L. Othman, K.B.M. Isa, Transport and morphological
properties of gel polymer electrolytes containing Mg(CF3SO3)2, Adv. Mater. Res.
686 (2013) 137–144.
[3] I. Riess, Polymeric mixed ionic electronic conductors, Solid State Ion. 136-137
(2000) 1119–1130.
[4] V. Parameswaran, N. Nallamuthu, P. Devendran, E.R. Nagarajan, A. Manikandan,
Electrical conductivity studies on Ammonium bromide incorporated with
Zwitterionic polymer blend electrolyte for battery application, Phys. B Condens.
Matter 515 (2017) 89–98.
[5] M.F. Shukur, M.H. Hamsan, M.F.Z. Kadir, Investigation of plasticized ionic
conductor based on chitosan and ammonium bromide for EDLC application, Mater.
Today Proc. 17 (2019) 490–498.
[6] J.M. Hadi, S.B. Aziz, M.F.Z. Kadir, Y.A. El-Badry, T. Ahamad, E.E. Hussein, A.S.F.
M. Asnawi, R.M. Abdullah, S.M. Alshehri, Design of plasticized proton conducting
chitosan: dextran based biopolymer blend electrolytes for EDLC application:
structural, impedance and electrochemical studies, Arab. J. Chem. 14 (2021),
103394.
[7] S.B. Aziz, M.A. Brza, E.M.A. Dannoun, M.H. Hamsan, J.M. Hadi, M.F.Z. Kadir, R.
T. Abdulwahid, The study of electrical and electrochemical properties of
magnesium ion conducting CS: PVA based polymer blend electrolytes: role of
lattice energy of magnesium salts on EDLC performance, Molecules 25 (2020)
4503.
[8] I. Stepniak, M. Galinski, K. Nowacki, M. Wysokowski, P. Jakubowska, V.
V. Bazhenov, T. Leisegang, H. Ehrlich, T. Jesionowski, A novel chitosan/sponge
chitin origin material as a membrane for supercapacitors—preparation and
characterization, RSC Adv. 6 (2016) 4007–4013.
[9] S.B. Aziz, O.G. Abdullah, S.A. Hussein, H.M. Ahmed, Effect of PVA blending on
structural and ion transport properties of CS:agNt based polymer electrolyte
membrane, Polymers 9 (2017) 622 (Basel).
13
Electrochimica Acta 461 (2023) 142659
[10] K. Sundaramahalingam, M. Muthuvinayagam, N. Nallamuthu, D. Vanitha,
M. Vahini, Investigations on lithium acetate-doped PVA/PVP solid polymer blend
electrolytes, Polym. Bull. 76 (2019) 5577–5602.
[11] A.L. Saroj, S. Krishnamoorthi, R.K. Singh, Structural, thermal and electrical
transport behaviour of polymer electrolytes based on PVA and imidazolium based
ionic liquid, J. Non Cryst. Solids 473 (2017) 87–95.
[12] M.H. Buraidah, A.K. Arof, Characterization of chitosan/PVA blended electrolyte
doped with NH4I, J. Non Cryst. Solids 357 (2011) 3261–3266.
[13] Y.M. Yusof, H.A. Illias, M.F.Z. Kadir, Incorporation of NH4Br in PVA-chitosan
blend-based polymer electrolyte and its effect on the conductivity and other
electrical properties, Ionics 20 (2014) 1235–1245 (Kiel).
[14] M.M. Nofal, S.B. Aziz, J.M. Hadi, R.T. Abdulwahid, E.M.A. Dannoun, A.S. Marif,
S. Al-Zangana, Q. Zafar, M.A. Brza, M.F.Z. Kadir, Synthesis of porous proton ion
conducting solid polymer blend electrolytes based on PVA: CS polymers: structural,
morphological and electrochemical properties, Materials 13 (2020) 4890 (Basel).
[15] L. Du, B. Zhang, X. Wang, C. Dong, L. Mai, L. Xu, 3D frameworks in composite
polymer electrolytes: synthesis, mechanisms, and applications, Chem. Eng. J. 451
(2023), 138787.
[16] C. Maheshwaran, D.K. Kanchan, K. Gohel, K. Mishra, D. Kumar, Effect of Mg
(CF3SO3)2 concentration on structural and electrochemical properties of ionic
liquid incorporated polymer electrolyte membranes, J. Solid State Electrochem. 24
(2020) 655–665.
[17] Y.M. Yusof, M.F. Shukur, H.A. Illias, M.F.Z. Kadir, Conductivity and electrical
properties of corn starch–chitosan blend biopolymer electrolyte incorporated with
ammonium iodide, Phys. Scr. 89 (2014), 035701.
[18] K.H. Guan, N.K. Farhana, F.S. Omar, N.M. Saidi, S. Bashir, S. Ramesh, K. Ramesh,
Influence of tetraglyme towards magnesium salt dissociation in solid polymer
electrolyte for electric double layer capacitor, J. Polym. Res. 27 (2020) 116.
[19] A.R. Polu, R. Kumar, Preparation and characterization of PVA based solid polymer
electrolytes for electrochemical cell applications, Chin. J. Polym. Sci. 31 (2013)
641–648.
[20] A.R. Polu, R. Kumar, H.W. Rhee, Magnesium ion conducting solid polymer blend
electrolyte based on biodegradable polymers and application in solid-state
batteries, Ionics 21 (2015) 125–132 (Kiel).
[21] Y. Wang, Y. Wu, Z. Wang, L. Chen, H. Li, F. Wu, Doping strategy and mechanism
for oxide and sulfide solid electrolytes with high ionic conductivity, J. Mater.
Chem. A 10 (2022) 4517–4532.
[22] E.M.A. Dannoun, S.B. Aziz, R.T. Abdulwahid, S.I. Al-Saeedi, M.M. Nofal, N.
M. Sadiq, J.M. Hadi, Study of MC:dN-based biopolymer blend electrolytes with
inserted Zn-metal complex for energy storage devices with improved
electrochemical performance, Membranes 12 (2022) 769.
[23] A.S.F.M. Asnawi, S.B. Aziz, I. Brevik, M.A. Brza, Y.M. Yusof, S.M. Alshehri,
T. Ahamad, M.F.Z. Kadir, The study of plasticized sodium ion conducting polymer
blend electrolyte membranes based on chitosan/dextran biopolymers: ion
transport, structural, morphological and potential stability, Polymers 13 (2021)
383 (Basel).
[24] D. Zhang, X. Zhang, Y. Chen, P. Yu, C. Wang, Y. Ma, Enhanced capacitance and rate
capability of graphene/polypyrrole composite as electrode material for
supercapacitors, J. Power Sources 196 (2011) 5990–5996.
[25] M. Inagaki, H. Konno, O. Tanaike, Carbon materials for electrochemical capacitors,
J. Power Sources 195 (2010) 7880–7903.
[26] M.F. Shukur, R. Ithnin, H.A. Illias, M.F.Z. Kadir, Proton conducting polymer
electrolyte based on plasticized chitosan–PEO blend and application in
electrochemical devices, Opt. Mater. 35 (2013) 1834–1841.
[27] V. Subramanian, H. Zhu, B. Wei, Nanostructured manganese oxides and their
composites with carbon nanotubes as electrode materials for energy storage
devices, Pure Appl. Chem. 80 (2008) 2327–2343.
[28] P. Naskar, D. Kundu, A. Maiti, P. Chakraborty, B. Biswas, A. Banerjee, Frontiers in
hybrid ion capacitors: a review on advanced materials and emerging devices,
Chem. Electro. Chem. 8 (2021) 1393–1429.
[29] Z.S. Iro, C. Subramani, S.S. Dash, A brief review on electrode materials for
supercapacitor, Int. J. Electrochem. Sci. 11 (2016) 10628–10643.
[30] J. Liu, Z. Khanam, R. Muchakayala, S. Song, Fabrication and characterization of
Zn-ion-conducting solid polymer electrolyte films based on PVdF-HFP/Zn(Tf)2
complex system, J. Mater. Sci. Mater. Electron. 31 (2020) 6160–6173.
[31] J.M. Hadi, S.B. Aziz, M.S. Mustafa, M.A. Brza, M.H. Hamsan, M.F.Z. Kadir, H.
O. Ghareeb, S.A. Hussein, Electrochemical impedance study of proton conducting
polymer electrolytes based on PVC doped with thiocyanate and plasticized with
glycerol, Int. J. Electrochem. Sci. 15 (2020) 4671–4683.
[32] T. Machappa, M.V.N.A. Prasad, AC conductivity and dielectric behavior of
polyaniline/sodium metavenadate (PANI/NaVO3) composites, Phys. B Condens.
Matter 404 (2009) 4168–4172.
[33] K.K. Kumar, R. Brindha, M. Nandhini, M. Selvam, K. Saminathan, K. Sakthipandi,
Water-suspended graphene as electrolyte additive in zinc-air alkaline battery
system, Ionics 25 (2019) 1699–1706 (Kiel).
[34] S. Ramesh, H.M. Ng, R. Shanti, K. Ramesh, Studies on the influence of titania
content on the properties of poly(vinyl chloride)–poly (acrylonitrile)-based
polymer electrolytes, Polym. Technol. Eng. 52 (2013) 1474–1481.
[35] R.J. Klein, S. Zhang, S. Dou, B.H. Jones, R.H. Colby, J. Runt, Modeling electrode
polarization in dielectric spectroscopy: ion mobility and mobile ion concentration
of single-ion polymer electrolytes, J. Chem. Phys. 124 (2006), 144903.
[36] S.B. Aziz, M.H. Hamsan, M.A. Brza, M.F.Z. Kadir, S.K. Muzakir, R.T. Abdulwahid,
Effect of glycerol on EDLC characteristics of chitosan:methylcellulose polymer
blend electrolytes, J. Mater. Res. Technol. 9 (2020) 8355–8366.
S.B. Aziz et al.
[37] S.K. Shetty, Ismayil, S. Hegde, V. Ravindrachary, G. Sanjeev, R.F. Bhajantri, S.
P. Masti, Dielectric relaxations and ion transport study of NaCMC:naNO3 solid
polymer electrolyte films, Ionics 27 (2021) 2509–2525 (Kiel).
[38] W. Wang, P. Alexandridis, Composite polymer electrolytes: nanoparticles affect
structure and properties, Polymers 8 (2016) 387 (Basel).
[39] A. Szczesna-Chrzan, M. Marczewski, J. Syzdek, M.K. Kochaniec, M. Smolinski,
M. Marcinek, Lithium polymer electrolytes for novel batteries application: the
review perspective, Appl. Phys. A 129 (2023) 37.
[40] H.J. Woo, S.R. Majid, A.K. Arof, Dielectric properties and morphology of polymer
electrolyte based on poly(ε-caprolactone) and ammonium thiocyanate, Mater.
Chem. Phys. 134 (2012) 755–761.
[41] N. Tripathi, A. Shukla, A.K. Thakur, D.T. Marx, Dielectric modulus and
conductivity scaling approach to the analysis of ion transport in solid polymer
electrolytes, Polym. Eng. Sci. 60 (2020) 297–305.
[42] C. Thirmal, S.D. Ramarao, L.S. Rao, V.R.K. Murthy, Study of structural, dielectric
and AC conductivity properties of SrMoO4, Mater. Res. Bull. 146 (2022), 111618.
[43] D.K. Pradhan, R.N.P. Choudhary, B.K. Samantaray, Studies of dielectric relaxation
and AC conductivity behavior of plasticized polymer nanocomposite electrolytes,
Int. J. Electrochem. Sci. 3 (2008) 597–608.
[44] J.C. Daigle, A.A. Arnold, A. Vijh, K. Zaghib, Solid-state NMR study of new
copolymers as solid polymer electrolytes, Magnetochemistry 4 (2018) 13.
[45] M.S. Mustafa, H.O. Ghareeb, S.B. Aziz, M.A. Brza, S. Al-Zangana, J.M. Hadi, M.F.
Z. Kadir, Electrochemical characteristics of glycerolized PEO-based polymer
electrolytes, Membranes 10 (2020) 116.
[46] H. Manjunatha, R. Damle, K. Pravin, G.N. Kumaraswamy, Modification in the
transport and morphological properties of solid polymer electrolyte system by low-
energy ion irradiation, Ionics 24 (2018) 3027–3037 (Kiel).
[47] M. Moreno, R. Quijada, M.A. Santa Ana, E. Benavente, P. Gomez-Romero,
G. González, Electrical and mechanical properties of poly(ethylene oxide)/
intercalated clay polymer electrolyte, Electrochim. Acta 58 (2011) 112–118.
[48] S.F. Cherif, A. Cherif, W. Dridi, M.F. Zid, Ac conductivity, electric modulus
analysis, dielectric behavior and bond valence sum analysis of Na3Nb4As3O19
compound, Arab. J. Chem. 13 (2020) 5627–5638.
[49] C.S. Ramya, S. Selvasekarapandian, G. Hirankumar, T. Savitha, P.C. Angelo,
Investigation on dielectric relaxations of PVP–NH4SCN polymer electrolyte, J. Non
Cryst. Solids 354 (2008) 1494–1502.
[50] S.A. Suthanthiraraj, D.J. Sheeba, B.J. Paul, Impact of ethylene carbonate on ion
transport characteristics of PVdF–AgCF3SO3 polymer electrolyte system, Mater.
Res. Bull. 44 (2009) 1534–1539.
[51] P. Basak, S.V. Manorama, R.K. Singh, O. Parkash, Investigations on the
mechanisms of ionic conductivity in PEO− PU/PAN semi-interpenetrating polymer
network− salt complex polymer electrolytes: an impedance spectroscopy study,
J. Phys. Chem. B 109 (2005) 1174–1182.
[52] H. Hassib, A.A. Razik, Dielectric properties and AC conduction mechanism for 5,7-
dihydroxy-6-formyl-2-methylbenzo-pyran-4-one bis-schiff base, Solid State
Commun. 147 (2008) 345–349.
[53] A.N. Papathanassiou, Novel feature of the universal power law dispersion of the ac
conductivity in disordered matter, J. Non Cryst. Solids 352 (2006) 5444–5445.
[54] N.J. Jo, M.K. Kim, S.W. Kang, K.S. Ryu, The influence of the cations of salts on the
electrochemical stability of a solid polymer electrolyte based on segmented poly
(ether urethane), Phys. Scr. 2010 (2010), 014035.
14
Electrochimica Acta 461 (2023) 142659
[55] S. Kiruthika, M. Malathi, S. Selvasekarapandian, K. Tamilarasan, T. Maheshwari,
Conducting biopolymer electrolyte based on pectin with magnesium chloride salt
for magnesium battery application, Polym. Bull. 77 (2020) 6299–6317.
[56] M.H. Hamsan, S.B. Aziz, M.F.Z. Kadir, M.A. Brza, W.O. Karim, The study of EDLC
device fabricated from plasticized magnesium ion conducting chitosan based
polymer electrolyte, Polym. Test. 90 (2020), 106714.
[57] M.H. Hamsan, S.B. Aziz, M.M. Nofal, M.A. Brza, R.T. Abdulwahid, J.M. Hadi, W.
O. Karim, M.F.Z. Kadir, Characteristics of EDLC device fabricated from plasticized
chitosan:mgCl2 based polymer electrolyte, Mater. Res. Technol. 9 (2020)
10635–10646.
[58] N.E.A. Shuhaimi, N.A. Alias, S.R. Majid, A.K. Arof, Electrical double layer capacitor
with proton conducting K-carrageenan–chitosan electrolytes, Funct. Mater. Lett. 1
(2009) 195–201.
[59] R. Brindha, R. Mohanraj, P. Manojkumar, M. Selvam, K. Sakthipandi, Hybrid
electrochemical behaviour of La1-xCaxMnO3 nano perovskites and recycled polar
interspersed graphene for metal-air battery system, J. Electrochem. Soc. 167
(2020), 120539.
[60] B. Pal, S. Yang, S. Ramesh, V. Thangadurai, R. Jose, Electrolyte selection for
supercapacitive devices: a critical review, Nanoscale Adv. 1 (2019) 3807–3835.
[61] J. Deng, J. Li, Z. Xiao, S. Song, L. Li, Studies on possible ion-confinement in
nanopore for enhanced supercapacitor performance in 4 V EMIBF4 ionic liquids,
Nanomaterial 9 (2019) 1664.
[62] M.Y. Chong, A. Numan, C.W. Liew, H.M. Ng, K. Ramesh, S. Ramesh, Enhancing the
performance of green solid-state electric double-layer capacitor incorporated with
fumed silica nanoparticles, J. Phys. Chem. Solids 117 (2018) 194–203.
[63] S. Pohlmann, T. Olyschlager, P. Goodrich, J.A. Vicente, J. Jacquemin, A. Balducci,
Mixtures of azepanium based ionic liquids and propylene carbonate as high voltage
electrolytes for supercapacitors, Electrochim. Acta 153 (2015) 426–432.
[64] M.H. Hamsan, M.F. Shukur, S.B. Aziz, Y.M. Yusof, M.F.Z. Kadir, Influence of NH4Br
as an ionic source on the structural/electrical properties of dextran-based
biopolymer electrolytes and EDLC application, Bull. Mater. Sci. 43 (2020) 30.
[65] A. Ajina, D. Isa, Symmetrical supercapacitor using coconut shell-based activated
carbon, Pertanika J. Sci. Technol. 18 (2010) 351. -163.
[66] M.F. Shukur, R. Ithnin, M.F.Z. Kadir, Electrical characterization of corn starch-
LiOAc electrolytes and application in electrochemical double layer capacitor,
Electrochim. Acta 136 (2014) 204–216.
[67] M. Hina, S. Bashir, K. Kamran, S. Ramesh, K. Ramesh, Synthesis and
characterization of self-healable poly (acrylamide) hydrogel electrolytes and their
application in fabrication of aqueous supercapacitors, Polymer 210 (2020), 123020
(Guildf).
[68] N. Mazuki, A.P.P. Abdul Majeed, A.S. Samsudin, Study on electrochemical
properties of CMC-PVA doped NH4Br based solid polymer electrolytes system as
application for EDLC, J. Polym. Res. 27 (2020) 135.
[69] J.M. Hadi, S.B. Aziz, H.G. Rauf, R.T. Abdulwahid, S.I. Al-Saeedi, D.A. Tahir, M.F.
Z. Kadir, Proton conducting polymer blend electrolytes based on MC: FTIR, ion
transport and electrochemical studies, Arab. J. Chem. 15 (2022), 104172.
[70] C. Zhong, Y. Deng, W. Hu, J. Qiao, L. Zhang, J. Zhang, A review of electrolyte
materials and compositions for electrochemical supercapacitors, Chem. Soc. Rev.
44 (2015) 7484–7539.
[71] A. Muzaffar, M.B. Ahamed, K. Deshmukh, J. Thirumalai, A review on recent
advances in hybrid supercapacitors: design, fabrication and applications, Renew.
Sustain. Energy. Rev. 101 (2019) 123–145.