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Solid-State EDLC Device Based on Magnesium Ion-Conducting Biopolymer

Composite Membrane Electrolytes: Impedance, Circuit Modeling, Dielectric
Properties and Electrochemical Charact...

Article in Membranes · December 2020

DOI: 10.3390/membranes10120389

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 membranes
Article
Solid-State EDLC Device Based on Magnesium
Ion-Conducting Biopolymer Composite Membrane
Electrolytes: Impedance, Circuit Modeling,
Dielectric Properties and Electrochemical Characteristics
Ahmad S. F. M. Asnawi 1 , Shujahadeen B. Aziz 2,3, * , Salah R. Saeed 4 , Yuhanees M. Yusof 1 ,
Rebar T. Abdulwahid 2,5 , Shakhawan Al-Zangana 6 , Wrya O. Karim 7 and Mohd. F. Z. Kadir 8
1 Chemical Engineering Section, Universiti Kuala Lumpur Malaysian Institute of Chemical & Bioengineering
Technology (UniKL MICET), Alor Gajah 78000, Malacca, Malaysia;
asyafiq.asnawi@s.unikl.edu.my (A.S.F.M.A.); yuhanees@unikl.edu.my (Y.M.Y.)
2 Hameed majid Advanced Polymeric Materials Research Lab., Department of Physics, College of Science,
University of Sulaimani, Qlyasan Street, Sulaimani 46001, Iraq; rebar.abdulwahid@univsul.edu.iq
3 Department of Civil Engineering, College of Engineering, Komar University of Science and Technology,
Sulaimani 46001, Iraq
4 Charmo Research Center, Charmo University, Peshawa Street, Chamchamal, Sulaimani 46001, Iraq;
salah.saeed@charmouniversity.org
5 Department of Physics, College of Education, Old Campus, University of Sulaimani, Kurdistan Regional
Government, Sulaimani 46001, Iraq
6 Department of Physics, College of Education, University of Garmian, Kalar 46021, Iraq;
shakhawan.al-zangana@garmian.edu.krd
7 Department of Chemistry, College of Science, University of Sulaimani, Qlyasan Street, Sulaimani 46001, Iraq;
wrya.karim@univsul.edu.iq
8 Centre for Foundation Studies in Science, University of Malaya, Kuala Lumpur 50603, Malaysia;
mfzkadir@um.edu.my
* Correspondence: shujahadeenaziz@gmail.com




Received: 21 October 2020; Accepted: 29 November 2020; Published: 2 December 2020


Abstract: The polymer electrolyte based on Dx:Cs:Mg(CH3 COO)2 :Ni with three different glycerol
concentrations have been prepared. The impedance study has verified that the electrolyte with 42 wt.%
of glycerol (A3) has the highest ionic conductivity of 7.71 × 10−6 S cm−1 at room temperature. The ionic
conductivity is found to be influenced by the transport parameters. From the dielectric analysis, it was
shown that the electrolytes in this system obeyed the non-Debye behavior. The A3 electrolyte exhibited
a dominancy of ions (tion > te ) with a breakdown voltage of 2.08 V. The fabricated electrochemical
double layer capacitor (EDLC) achieved the specific capacitance values of 24.46 F/g and 39.68 F/g
via the cyclic voltammetry (CV) curve and the charge–discharge profile, respectively. The other
significant parameters to evaluate the performance of EDLC have been determined, such as internal
resistance (186.80 to 202.27 Ω) energy density (4.46 Wh/kg), power density (500.58 to 558.57 W/kg)
and efficiency (92.88%).

Keywords: ion conducting membrane; polymer blend; magnesium acetate; metal complex;
transport study; transference number measurement (TNM) and linear sweep voltammetry (LSV)
analyses; energy storage device

1. Introduction
The studies on solid polymer electrolytes have shown an excellent performance in electrochemical
devices applications such EDLCs [1,2]. These devices can provide a higher power and energy densities

Membranes 2020, 10, 389; doi:10.3390/membranes10120389 www.mdpi.com/journal/membranes

Membranes 2020, 10, 389 2 of 20

compared to batteries, and makes them functional in many applications such as hybrid vehicles,
electronics, and voltage stabilizers [1,2]. On the other hand, with a simple and economical fabrication
procedure, EDLCs have been acknowledged to offer an adequate performance which is found to
be a suitable candidate to replace a conventional battery [3–5]. In the fabrication process of EDLCs,
activated carbon is commonly chosen by researchers to build an electrode because it able to produce
high conductivity value and also has large surface area [6]. Furthermore, the fermentation process of
leuconostoc mesenteroides bacteria could grow a natural polymer called dextran (Dx), which has been
recently used in the preparation of solid polymer electrolyte [7–9]. The various oxygen functional groups
at the 1,6-α-D-glucopyranosidic linkages in Dx polymer chain helps to enhance the ionic conductivity
of the system [10]. Besides, chitosan (Cs) is also one of the natural polymers that are produced
from deacetylation of chitin and typically used in this field of research. The properties possessed
by Cs, such as low toxicity, biodegradability and biocompatibility, make it more preferable than other
polymers to be used in the preparation of solid polymer electrolyte [11,12]. Cs contains numerous
functional groups such as acetamido, amino and hydroxyl groups that could form interactions with
dative bonds as well as act as an electron donor [13,14]. The solid polymer electrolytes have also been
widely employed in electrochemical devices because they have good film forming ability, in addition
to desired mechanical and thermal characteristics [15,16]. Through polymer blending, more room will
be available for the ions to hope within the long lasting solid polymer electrolytes, which result in
rising the conductivity [17,18].
The ionic conductivity of an electrolyte is one of the significant factors to determine the performance
of the EDLCs. Many factors have been investigated, which might affect the ionic conductivity of
an electrolyte such as salt, plasticizer and metal complex. The good performance of Li+ ion-based
salt might have few drawbacks towards the ecosystem because they are not biodegradable [19].
Consequently, some alternatives have been introduced and applied to replace the Li+ ion in the
polymer electrolyte, such as NH4 + and Mg2+ ions [20,21]. Syahidah et al. [22] stated that Mg(CF3 SO3 )2
salt is suitable to be used in polymer electrolyte because it is cost effective, abundance and also
easy to handle. Moreover, it was shown that the plasticized type of polymer electrolyte might
experience higher ionic conductivity [23]. This hypothesis has been proven in other polymer electrolyte
studies that using glycerol as the plasticizer for the system [24–26]. This is due to the glycerol ability
to produce more ionic pathways within the electrolyte that highly impacts the performance of an
electrochemical device [27,28]. In addition, the polymer electrolyte with metal complex also found to
achieve higher ionic conductivity by improving the amorphous phase of the system [29]. Brza et al. [29]
reported that the amorphousness of the PVA-based electrolyte was enhanced with the incorporation of
Cu(II)-complex by reducing the energy band gap and described as very beneficial for the application
of electrochemical devices.
Our previous work studied the effect of Zn(II)-complex in the chitosan-NH4 F-glycerol system and
proved that the Zn metal assisted in enhancing the amorphousness of the electrolyte [30]. From the
above mentioned statements, these three elements are crucial to improve the characteristics of an
electrolyte especially the one that will be applied in the EDLC. In this current work, the blend of
40 wt.% Dx and 60 wt.% Cx is chosen to serve as the polymer host for this system because based on our
previous work [9,31], this composition was the most amorphous blend. The different concentration of
glycerol was added in the Dx-Cs based polymer electrolyte that complexed with magnesium acetate,
Mg(CH3 COO)2 and nickel, Ni metal. Lastly, the EDLC will be fabricated by choosing the highest
conducting polymer electrolyte based on several parameters.

2. Experimental Details

2.1. Sample Preparation

All the chemical materials were bought from Sigma-Aldrich (Kuala Lumpur, Malaysia) and directly
used for the sample preparation. The polymer blend host was prepared by separately dissolving 0.4 g Dx
Membranes 2020, 10, 389 3 of 20

(average molecular weight 35,000–45,000) and 0.6 g Cs (average molecular weight 310,000–375,000) in
50 mL of 1% acetic acid for 90 min under an ambient temperature level. These two different solutions
were mixed and stirred constantly for about 3 h at room temperature to obtain a homogeneous solution.
Next, 40 wt.% of
Membranes Mg(CH
2020, 10, x FOR3 COO) 2 salt was added to the polymer blend solution, which then
PEER REVIEW 3 of stirred
21 at
room temperature to obtain a homogeneous solution. Then, 10 mL of Ni metal was incorporated to the
dissolving 0.4 g Dx (average molecular weight 35,000–45,000) and 0.6 g Cs (average molecular weight
solutions. Subsequently, different concentration of glycerol was separately added to the electrolyte
310,000–375,000) in 50 mL of 1% acetic acid for 90 min under an ambient temperature level. These
system two
anddifferent
labeledsolutions
as A1, A2 andmixed
were A3 for the
and addition
stirred glycerol
constantly at the3concentration
for about of 14, 28,
h at room temperature and 42 wt.%,
to obtain
respectively. The solutions
a homogeneous solution.were then
Next, casted
40 wt.% of in clean3COO)
Mg(CH and 2dry
saltlabeled Petri
was added to dishes and left
the polymer blend to dry at
solution, which
room temperature forthen stirred
films at room
to form. temperature
Table 1 displaysto obtain a homogeneous
the composition of solution. Then, 10films.
the electrolyte mL of
Ni metal was incorporated to the solutions. Subsequently, different concentration of glycerol was
separately added
Table to the electrolyte
1. Designation of thesystem
polymerand labeled as A1,
electrolytes withA2 and A3 amount
different for the addition glycerol at
of glycerol.
the concentration of 14, 28, and 42 wt.%, respectively. The solutions were then casted in clean and
dry labeled Petri dishes and left toGlycerol
dry at (wt.%) Designation
room temperature for films to form. Table 1 displays the
composition of the electrolyte films. 12 A1
28 A2
42
Table 1. Designation of the polymer A3 different amount of glycerol.
electrolytes with

Glycerol (wt.%) Designation

2.2. Characterization Methods 12 A1
28 A2 impedance properties, which carried out
The prepared electrolytes were first tested to study the
42 A3
within the frequency range of 50 Hz to 5 MHz by using a LCR meter (HIOKI 3531 Z Hi-tester, Nagano,
Japan) at
2.2.room temperature.
Characterization From the recorded impedance data, the ionic conductivity of an electrolyte
Methods
can be determined by employing the Equation (1) below.
The prepared electrolytes were first tested to study the impedance properties, which carried out
within the frequency range of 50 Hz to 5 MHz by using1 a LCR
t meter (HIOKI 3531 Z Hi-tester, Nagano,
σdc = impedance
Japan) at room temperature. From the recorded × data, the ionic conductivity of an (1)
Rb A
electrolyte can be determined by employing the Equation (1) below.
where the bulk resistance, Rb was determined from 1 the 𝑡 intercept of the Cole–Cole plot at the Zr
𝜎𝑑𝑐 = × (1)
axis while t and A represent the thickness and surface 𝑅 𝑏 𝐴 area of the polymer composite electrolyte.
Furthermore,
where the the
bulktransference
resistance, Rbnumber measurement
was determined from the (TNM)
interceptofof the ionic (tionplot
the Cole–Cole ) and electronic
at the Zr axis (telec )
while
were also t and A in
identified represent the by
this study thickness
using and surface
the cell area of theplot
polarization polymer
of currentcomposite electrolyte.
against time at room
Furthermore,
temperature. The theTNM transference
study was number
onlymeasurement
carried out (TNM) of the
for the ionic (tion
highest ) and electronic
conducting (telec) were where
electrolyte
also identified in this study by using the cell polarization plot of current against time at room
it was placed in a teflon holder using similar stainless steel electrodes as illustrated in Figure 1.
temperature. The TNM study was only carried out for the highest conducting electrolyte where it
The instrument used to conduct this measurement was the V&A Instrument DP3003 with a digital
was placed in a teflon holder using similar stainless steel electrodes as illustrated in Figure 1. The
DC power supply
instrument (Shanghai,
used to conductChina) and the system
this measurement was thewas V&Apolarized
InstrumentatDP3003a workingwith avoltage
digital DC of 0.20 V
under an ambient
power supplytemperature condition.
(Shanghai, China) and theIn addition,
system the electrochemical
was polarized stability
at a working voltage of an
of 0.20 V electrolyte
under is
an ambient temperature condition. In addition, the electrochemical stability
also a significant characteristic to study. This can be obtained by using a linear sweep voltammetryof an electrolyte is also a
significant
(LSV) where characteristic
it can record thetodecomposition
study. This can be obtained
voltage of by
an using a linearatsweep
electrolyte roomvoltammetry
temperature. (LSV)
A similar
where it can record the decomposition voltage of an electrolyte at room temperature. A similar
electrolyte–electrodes arrangement as in TNM study was utilized with an involvement of the highest
electrolyte–electrodes arrangement as in TNM study was utilized with an involvement of the highest
conducting electrolyte only. A DY2300 potentiostate (Digi-Ivy, Neware, Shenzhen, China) was used to
conducting electrolyte only. A DY2300 potentiostate (Digi-Ivy, Neware, Shenzhen, China) was used
record the LSV responses
to record towards the
the LSV responses electrolyte
towards at 10 mV/s.
the electrolyte at 10Figure
mV/s. 1Figure
shows1ashows schematic illustration of
a schematic
the electrolyte–electrodes arrangement for both TNM and LSV analyses.
illustration of the electrolyte–electrodes arrangement for both TNM and LSV analyses.

Electrolyte

Stainless steel Teflon case

Figure 1. Schematic illustration of the electrolyte–electrodes arrangement for TNM and LSV studies.
Membranes 2020, 10, x FOR PEER REVIEW 4 of 21
Membranes 2020, 10, 389 4 of 20
Figure 1. Schematic illustration of the electrolyte–electrodes arrangement for TNM and LSV studies.

EDLC Fabrication
2.3. EDLC Fabrication
The EDLC was fabricated by preparing the activated carbon (AC) electrode electrode where 0.25 g AC
was mixed with 3.25 g carbon black in the planetary ball miller. For this purpose, the powders with
metal balls
six metal ballswere
wereput
putininthe
thechamber.
chamber.The
The powders
powders were
were mixed
mixed at rotational
at rotational speed
speed of 500
of 500 r/min
r/min for
for min.
15 15 min. Simultaneously,
Simultaneously, 0.500.50 g polyvinylidene
g polyvinylidene fluoride
fluoride (PVdF)was
(PVdF) wasdiluted
dilutedinin15
15 mL
mL N-methyl
pyrrolidone (NMP). Then, the mixture from ball miller was poured into the PVdF-NMP solution and
was stirred to obtain a thick, black solution. Consequently, an amount of acetone was used to clean
an aluminum foil which then flattened on a glass surface. The The prepared black solution
solution was evenly
spread on the surface of aluminum foil using doctor blade technique. It was left to dry in oven under
temperature of 60 ◦°CC and then was placed in a desiccator for further drying. The arrangement of the
highest conducting electrolyte
electrolyte and
and AC
AC electrodes
electrodes in
in the
the EDLC
EDLC is shown in Figure 2 by using a CR2032
coin cell.

Electrolyte

Anode Cathode

Stainless steel Teflon case

Figure
Figure 2.
2. Schematic
Schematic illustration
illustration of
of the
the fabricated
fabricated EDLC
EDLC for
for characterization.
characterization.

3. Results
3. Results and
and Discussion
Discussion

3.1. Impedance
3.1. Impedance Study
Study
The impedance
The impedance plot plot of
of the
the electrolyte
electrolyte with
with various
various glycerol
glycerol concentrations
concentrations at at room
room temperature
temperature
is depicted in Figure 3 where a spike and a semicircle is noted to exist at low and
is depicted in Figure 3 where a spike and a semicircle is noted to exist at low and high frequencies, high frequencies,
respectively [32].
respectively [32]. The
The semicircle
semicircle arc
arc is
is due
due to
to the
the conduction
conduction of of charges
charges inin the
the bulk
bulk of
of the
the electrolyte
electrolyte
that corresponds to the parallel combination of R and a constant phase
that corresponds to the parallel combination of Rbb and a constant phase element (CPE1), whileelement (CPE1), while the
the
spike represents the accumulation of charge in polarization process that represented
spike represents the accumulation of charge in polarization process that represented by CPE2, which by CPE2, which is
also
is a feature
also a featureof of
a diffusion
a diffusionmechanism
mechanism [33,34].
[33,34].It is clearly
It is detected
clearly detectedthat
thatthethe
semicircle
semicirclein in
Figure
Figure3 is
3
getting smaller with the addition of glycerol, which attributed to prevalence of the
is getting smaller with the addition of glycerol, which attributed to prevalence of the resistive part in resistive part in
the electrolyte,
the electrolyte, hence
hence causing
causing the
the intercept
intercept ofof R with Z
Rbb with axis to
Zrr axis to decrease
decrease [35]. The impedance
[35]. The impedance of of CPE
CPE
(Z CPE ) can be expressed as [36,37]:
(ZCPE) can be expressed as [36,37]:
11  𝜋𝑝 πp   πp
𝜋𝑝
𝑍𝐶𝑃𝐸
ZCPE =
= [cos
cos( ) −
− 𝑖
i sin ( )] (2)
(2)
Cω𝑝p
𝐶𝜔 22 22
where C
where C is
is the
the capacitance
capacitance of CPE,ω𝜔isisthe
of CPE, theangular
angular frequency
frequency and
and p is
p is associated
associated with
with thethe deviation
deviation of
of the plot from the axis. For the plots that consist of semicircle and spike, the Zr and Zi of the
the plot from the axis. For the plots that consist of semicircle and spike, the Zr and Zi of the equivalent
equivalent
circuits cancircuits can be
be obtained viaobtained via theequations:
the following following equations:
𝜋𝑝 𝜋𝑝
𝑅𝑏 𝐶1 𝜔 𝑝p1 cos ( πp11) + 𝑅𝑏 cos(πp2 2 )
R C ω 1 cos 2 + R cos 2
𝑍𝑟 = b 1 2 b + 2𝑝 (3)
Zr =2𝑅𝑏 𝐶1 𝜔 𝑝1 cos (𝜋𝑝 1 2 2 2𝑝1 + 𝐶 𝜔 2 (3)
1 ) + 𝑅2 𝑏 𝐶1 𝜔2p + 1
πp 2 p
p 1 2
2Rb C1 ω cos 2 + Rb C1 ω + 1 2 1 C 2 ω 2
Membranes 2020, 10, 389 5 of 20

Membranes 2020, 10, x FOR PEER REVIEW 5 of 21

 πp   πp 
R2b2C1 ω𝑝p11 sin 𝜋𝑝2 11 sin𝜋𝑝22 2
Zi = 𝑅𝑏 𝐶1𝜔 sin  ( 2 ) +sin ( 2 p)2 (4)
p1 cos πp
𝐶2C𝜔2 𝑝ω2
𝑍𝑖 = 2 C2 ω2p1 + 1+ (4)
2Rb C1 ω 𝑝 𝜋𝑝 1
1 + R 2
2𝑅 𝐶 𝜔 1 cos ( 2 ) + 𝑅b 𝐶 1𝜔 1 + 12 2𝑝
𝑏 1 2 𝑏 1

p2 and
wherewhere p1 are
p2 and thethe
p1 are deviation
deviationofofthe
thespike
spike from thehorizontal
from the horizontalaxis
axis and
and deviation
deviation semicircle
semicircle from from
the vertical axis, respectively. The capacitances at high and low frequency are represented as C
the vertical axis, respectively. The capacitances at high and low frequency are represented as C1 1and and C2 ,
respectively. The determined
C2, respectively. Rb value
The determined and and
Rb value calculated CPE
calculated values
CPE valuesare
aretabulated
tabulated in Table 2.
in Table 2.

1 25
(A1) Experimental (A2) Experimental
Fitting Fitting
0.8 20
Rb
Rb
Zi x 10 (Ω)

Zi x 10 (Ω)
0.6 15
6

3
0.4
CPE2
CPE2 10 CPE1
CPE1
0.2 5

0 0
0 0.2 0.4 0.6 0.8 1 0 5 10 15 20 25
Zr x 106 (Ω) 3
Zr x 10 (Ω)

10
Experimental
(A3) Fitting
8 Rb
Zi x 10 (Ω)

6
3

CPE2
4
CPE1

0
0 2 4 6 8 10
3
Zr x 10 (Ω)

Figure 3. Cole–Cole
Figure plotplot
3. Cole–Cole forfor
(A1),
A1, (A2) and
A2 and A3(A3) electrolytes.
electrolytes.
Table 2. The parameter of circuit element for the electrolyte system with different glycerol concentration
Table 2. The parameter of circuit element for the electrolyte system with different glycerol
at room temperature.
concentration at room temperature.
Electrolyte
Electrolyte RR
b (Ω)
b (𝛀)
CPE1(F)
CPE1 (F) CPE2
CPE2 (F)(F)
A1 A1 3.00
3.00 5 5
× ×1010 5.00
5.00 ×× 10 −10
10−10 5.88 × 10
5.88 −7 −7
× 10
A2 A2 5.80
5.80 3 3
× ×1010 2.50 × 10−9−9
2.50 × 10 5.56 × 10−6 −6
5.56 × 10
A3 A3 2.00 × 10 3
2.00 × 103 3.33 10−9−9
3.33 ×× 10 6.06
6.06 × 10
× 10 −6
−6

Based on Table 2, the value of CPE is higher at low frequency compared to high frequency. This
Based on Table
phenomenon 2, the value
corresponds to the of CPE isequation:
following higher at low frequency compared to high frequency.
This phenomenon corresponds to the following equation:

εo εr A
C= (5)
d
Membranes 2020, 10, 389 6 of 20

where d is the thickness of the polymer composite electrolyte while A symbolizes the contact area. εr and
εo stand for dielectric constant and vacuum’s permittivity. The value of εr is high at lower frequency
region which in turn giving a high value of C [38]. According to Guan et al. [39], the divalent Mg2+
ion has attracted towards the lone pair of oxygen atoms while the CH3 COO− anion has delocalized
negative charges, which can be stabilized by the resonance stabilization and makes it as a good leaving
group. This phenomenon is beneficial for the ion dissociation hence, enhance the ionic mobility and
conductivity [40]. From the obtained Rb values in Table 2, the ionic conductivity of the electrolytes at
room temperature can be calculated using the Equation (1) as listed in Table 3.

Table 3. Ionic conductivity for the electrolyte system with different glycerol concentration at room temperature.

Electrolyte Ionic Conductivity, σ (S cm−1 )

A1 5.14 × 10−8
A2 2.66 × 10−6
A3 7.71 × 10−6

The addition of glycerol into the electrolyte able to improve room temperature conductivity of the
current system, which optimized at the highest value of 7.71 × 10−6 S cm−1 that possessed by the A3
electrolyte. This achievement can realize the electrolyte as a promising magnesium ion conductor for
the electrochemical devices applications. The ionic conductivity in this work is influenced by several
variables where their correlation can be expressed as:

σ = µne (6)

where µ, n and e are the concentration of the mobility of ions, number density of free ions and the
charge of electron, respectively [41]. The ionic conductivity increment of the electrolyte is caused by the
increase in the number of n and µ and the reduction of potential barrier in the system, which correlated
with the enhancement of the amorphous nature of the electrolyte. The glycerol plasticizer can dissociate
more salts and disrupt hydrogen bonding between polymer chains [25,27]. Thus, this improve the
overall amorphous phase of the prepared samples, which acts as a pathway for ion conduction [25,27].
Additionally, more free ions will be available for conduction. The impedance study is support this
interpretation. Besides, the CH3 COO− anion will penetrate into the polymer matrix and create an
attractive force between plasticizer molecules and chain segments where these forces will reduce the
cohesive attraction between polymer chains that caused the segmental mobility to increase hence
further enhance the ionic conductivity [42].

3.2. Dielectric and Electric Modulus Studies

To more understanding the polarization effects and the conductivity performance of the electrolyte
system, dielectric analysis is carried out. The dielectric constant, εr signifies the charge stored and the
dielectric loss, εi is the value of energy loss during the ions movement within the electrolytes [43].
The values of dielectric loss and dielectric constant can be calculated using the following expressions
where the vacuum capacitance, Co is included.

Zi
εr =   (7)
Z2r + Z2i Co ω

Zr
εi =   (8)
Z2r + Z2i Co ω
The plots of both dielectric properties are shown in Figure 4. The highest conducting electrolyte,
A3 is observed to achieve the highest dielectric properties values at a lower frequency but then
decreases as the frequency increased. This displays that the addition of glycerol may supports in
Membranes 2020, 10, 389 7 of 20

Membranes 2020, 10, x FOR PEER REVIEW 7 of 21

enhancing the dielectric values and the number of free ions. The high values achieved from this
enhancing the dielectric values and the number of free ions. The high values achieved from this
dielectric study described the space charge effects as well as the electrode polarization that contributed
dielectric study described the space charge effects as well as the electrode polarization that
by the accumulation of charge carriers [44,45]. This phenomenon explained that the electrolytes in this
contributed by the accumulation of charge carriers [44,45]. This phenomenon explained that the
work obeyed the non-Debye behavior. However, the decrement of dielectric values at high frequency
electrolytes in this work obeyed the non-Debye behavior. However, the decrement of dielectric values
may due to the rapid periodic reversal of the electric field [46]. Besides, the plots of dielectric properties
at high frequency may due to the rapid periodic reversal of the electric field [46]. Besides, the plots of
also did not properties
dielectric exhibit any peaks
also of dielectric
did not relaxation,
exhibit any peaks of which means
dielectric the system
relaxation, whichismeans
dominantly due to
the system
theispolymer
dominantly due to the polymer relaxation segments in the ionic conductivity [47]. The dielectric is
relaxation segments in the ionic conductivity [47]. The dielectric loss tangent (tanδ)
plotted as in Figure
loss tangent (tanδ)5istoplotted
solve the
as inrelaxation processes.
Figure 5 to solve the relaxation processes.

60,000
A1
A2
A3
40,000
er

20,000

0
1 2 3 4 5 6 7
Log f (Hz)
(a)
60,000

A1
A2
40,000 A3
ei

20,000

0
1 2 3 4 5 6 7
Log f (Hz)

(b)
Figure4.4.The
Theplot
plotof (a) ε𝜀𝑟 and
of (a) (b) 𝜀 for the electrolyte system.
Figure r and (b) ε𝑖i for the electrolyte system.
 The tan δ is a ratio of energy dissipate to energy stored in a periodical field, which is also known
as dissipation factor [48]. The value of tan δ can be calculated this equation:
𝜀𝑖
tan 𝛿 = (9)
Membranes 2020, 10, 389 𝜀𝑟 8 of 20

20
A1
A2
15
A3
tan d

10

0
1 2 3 4 5 6 7
Log f (Hz)
Figure 5. The plot of tan δ with respect to log f.
Figure 5. The plot of tan 𝛿 with respect to log f.
The tan δ is a ratio of energy dissipate to energy stored in a periodical field, which is also known
Basedas on Figurefactor
dissipation 5, the peaks
[48]. observed
The value of tan δ are explained
can be calculated as
thisthe translational ion dynamics that
equation:
related to the mobile ions conductivity relaxation which ε further explained the decrease in segmental
tan δ = i (9)
motion within the polymer electrolyte that beneficial to εr support the transportation of ions [49]. The
broad tan 𝛿 peaks in Figure 5 also signifies that the relaxation process is following non-Debye
Based on Figure 5, the peaks observed are explained as the translational ion dynamics that related
behavior [50].
to theFurthermore, the polarization
mobile ions conductivity relaxationsuppression
which further effect of the
explained the system
decrease can be analyzed
in segmental motion through
the electrical modulus
within as plotted
the polymer in that
electrolyte Figure 6. Thetoreal
beneficial partthe
support (Mtransportation
r) and imaginary
of ionspart
[49]. (M
Thei) broad
of electrical
modulus cantan δbe determined
peaks in Figure 5 using thesethat
also signifies relations:
the relaxation process is following non-Debye behavior [50].
Furthermore, the polarization suppression effect of the system can be analyzed through the electrical
𝜀𝑟
𝑀𝑟 =
modulus as plotted in Figure 6. The real part (Mr ) and imaginary part (Mi ) of electrical modulus can (10)
be determined using these relations: 𝜀𝑟 + 𝜀𝑖2
2
εr
Mr = 2𝜀𝑖 2 (10)
𝑀𝑖 = 2εr + ε2i (11)
𝜀𝑟 + 𝜀𝑖
ε
Mi = 2 i 2 (11)
At low frequencies, Mr and Mi approach εr +
to zero εi
because
the electrode polarization is dominant
and no dispersion
At lowisfrequencies,
observed [31].
Mr andLong tail at low
Mi approach frequencies
to zero because theindicates
electrode the capacitive
polarization behavior. The
is dominant
highest conducting electrolyte
and no dispersion will [31].
is observed produce
Long the lowest
tail at Mr and M
low frequencies i values
indicates theatcapacitive
a high frequency.
behavior. The
The highest conducting electrolyte will produce the lowest
presence of peaks in both modulus plots explain that the electrolytes M r and M values at a high frequency.
i are good ionic conductors at
The presence of peaks in both modulus plots explain that the electrolytes are good ionic conductors at
higher frequencies [51].
higher frequencies [51].
Membranes 2020, 10, 389 9 of 20
Membranes 2020, 10, x FOR PEER REVIEW 9 of 21

0.24
A1
A2
Mr 0.18 A3

0.12

0.06

0.00
1 2 3 4 5 6
Log f (Hz)
(a)

0.08
A1
A2
0.06 A3
Mi

0.04

0.02

0.00
1 2 3 4 5 6
Log f (Hz)
(b)
Figure
Figure 6.
6. The
Theplot
plotof
of(a)
(a) M
Mrrand
and(b)
(b)M
Mi ifor
forthe
theelectrolyte
electrolytesystem.
system.

3.3. Transport
3.3. Transport Study
Study
Based on
Based on Equation
Equation (6), two significant parameters, andµ,𝜇,are
parameters, nn and areimportant
importanttotoinfluence
influenceasaswell as
well
support
as supportthe ionic
the ionicconductivity
conductivityofofthe
theelectrolytes.
electrolytes.According
Accordingtoto Arof
Arof et al. [52], these
these ionic
ionictransport
transport
parameters can be evaluated
parameters evaluated using
usingthe theelectrical
electricalimpedance
impedancespectroscopy
spectroscopy (EIS) approach
(EIS) approachby by
fitting the
fitting
the impedance curve in Figure 3. This method expressed diffusion coefficient, D using the Equation
(12) for the Cole–Cole plots with semicircles and spikes.
Membranes 2020, 10, 389 10 of 20

impedance curve in Figure 3. This method expressed diffusion coefficient, D using the Equation (12)
for the Cole–Cole plots with semicircles and spikes.

(k2 εo εr A)2
D= (12)
τ2

The Equation (12) required the τ2 , which represents the inverse of ω at the minimum value of Zi .
Fadzallah et al. [53] mentioned that εr was taken from a constant value of log εr in the transport
study, while Yusof et al. [54] mentioned in their report that εr was taken at log f > 5 where the
values were almost constant. The µ values can be determined by substituting Equation (12) into the
following equation:
eD
µ= (13)
kB T
where kB and T are the Boltzmann constant and an absolute temperature, respectively. Table 4 provides
the values of p2 , k2 , εr and τ2 for the electrolytes in this work.

Table 4. The calculated values of p2 , k2 , εr and τ2 for the electrolyte system.

Electrolyte p2 k2 (F−1 ) εr τ2 (s)

A1 0.38 1.70 × 106 4.76 2.65 × 10−4
A2 0.49 1.80 × 105 10.64 5.89 × 10−6
A3 0.60 1.65 × 105 12.72 4.86 × 10−6

By using the Equations (6), (12) and (13), the transport parameter can be obtained as listed in
Table 5 for the electrolytes in this work. The trend of the transport parameters are harmonized with
the ionic conductivity pattern where the addition of glycerol helped to increase the values and the
highest conducting electrolyte possesses the highest transport parameters values. Pritam et al. [55]
also reported the similar trend where the increase in transport parameter values were possibly related
to the low degree of crystallinity of an electrolyte. Thus, this would improve the segmental motion
within the polymer chain, which therefore the electrolyte would achieve a high ionic conductivity [55].

Table 5. The calculated transport parameters for the electrolyte system.

Electrolyte n (cm−3 ) µ (cm2 V−1 s−1 ) D (cm2 s−1 )

A1 5.20 × 1019 6.17 × 10−9 1.58 × 10−10
A2 2.32 × 1021 7.14 × 10−9 1.83 × 10−10
A3 5.50 × 1021 8.75 × 10−9 2.25 × 10−10

3.4. Transference Number Measurement (TNM)

To determine which charge carrier species is dominant within the electrolytes, a measurement
called TNM was conducted in this work. Figure 7 shows the plot of current versus time for the A3
electrolyte. The electrolyte is mostly due to ions if the ionic transference number, tion value is larger
than the transference number of electron, te where these both values can be determined using the
following expressions that initial current, Ii and steady state current, Iss are involved [56].

Ii − Iss
tion = (14)
Ii

Iss
te = (15)
Ii
 Membranes 2020, 10, x FOR PEER REVIEW 11 of 21

has signified that the electrolyte consists of more ions compared to electrons and also agreed with
Membranes 2020, 10, 389 11 of 20
other studies [30,60].

400

300
Membranes 2020, 10, x FOR PEER REVIEW Ii 11 of 21

Current (mA)
has signified that the electrolyte consists of more ions compared to electrons and also agreed with
other studies [30,60].200

400
100
ISS

300
Ii
0
Current (mA)

0 100 200 300 400 500

200 Time (s)
Figure
Figure 7. The
7. The plotofofcurrent
plot current versus
versus time
timefor
forthe A3A3
the electrolyte.
electrolyte.

3.5. Linear
Based Sweep
on the Voltammetry
polarization
100 (LSV)in
plot Study
Figure 7, the Ii is noticed to drastically decrease as the time
ISS
increased.The This
LSVis because
study is the ionic
carried outspecies
to revealin the
the electrolyte
breakdown is dropped
voltage of anat electrolyte
this stage atand leading
room
towards Iss when[61].
temperature the Figure
species is completely
8 depicts reduced
the LSV plot up to [57]. Besides,
4.0 V for the A3 the decrement of ionic species is
electrolyte.
caused by the blockage of ions flows due to stainless steel electrodes that only allow the electron to
0
move [58]. The diffusion1.2 process is beneficial at Iss to balance the mobile ions movements [59]. In this
0 100 200 300 400 500
study, the A3 electrolyte achieved a high tion value which is 0.9936 while the te is 0.0064. This result has
signified that the electrolyte consists of more ions Time compared(s) to electrons and also agreed with other
studies [30,60].
Current density (mA/cm2) Current density (mA/cm2)

Figure 7. The plot of current versus time for the A3 electrolyte.

0.9
3.5. Linear Sweep
3.5. Linear Voltammetry
Sweep (LSV)
Voltammetry Study
(LSV) Study
The LSV
The LSV studystudy is carried
is carried outtotoreveal
out reveal the
the breakdown
breakdown voltage
voltageof of
an an
electrolyte at room
electrolyte at room
temperature [61]. Figure
temperature [61]. Figure0.6 8 depicts the LSV plot up to 4.0 V for the A3 electrolyte.
8 depicts the LSV plot up to 4.0 V for the A3 electrolyte.
Breakdown voltage = 2.08 V
1.2
0.3

0.9
0.0
0.0 1.0 2.0 3.0 4.0
0.6 Potential
Breakdown voltage = 2.08(V)
V
Figure 8. The plot of LSV curve for the A3 electrolyte.

0.3

0.0
0.0 1.0 2.0 3.0 4.0
Potential (V)
Figure
Figure 8. 8.
TheThe plotofofLSV
plot LSV curve
curve for
forthe
theA3
A3electrolyte.
electrolyte.
Membranes 2020, 10, 389 12 of 20

Membranes 2020, 10, x FOR PEER REVIEW 12 of 21

The plot of current density versus voltage as shown in Figure 8 reveals the raise of voltage
without
Theany
plotcurrent flows
of current involved
density untilvoltage
versus 2.08 V, as
which explain
shown that the
in Figure reactionthe
8 reveals of raise
electrochemical
of voltage
in the electrolyte
without any currentdidflows
not occur at this
involved untilstage
2.08 [62]. Thisexplain
V, which phenomenon
that theindicates that
reaction of the breakdown
electrochemical in
voltage of the did
the electrolyte electrolyte
not occur is at this
2.08stage
V, which
[62]. is comparable
This phenomenon as reported
indicatesinthat
thethe
literature
breakdown[63]. voltage
Hence,
this
of result
the showsisthat
electrolyte the ability
at 2.08 V, whichof this electrolyteas
is comparable toreported
deliver ainpromising performance
the literature [63]. Hence,in the
thisEDLC
result
that is normally
shows run at the
that the ability operating
of this voltage
electrolyte to of 1.0 V [64].
deliver a promising performance in the EDLC that is
normally run at the operating voltage of 1.0 V [64].
3.6. Characterization of the EDLC
3.6. Characterization of the EDLC
The cyclic voltammetry (CV) measurement is one of the crucial analyses to identify the charge
storage
Theand charge
cyclic transfer behaviors
voltammetry in the fabricated
(CV) measurement is one ofEDLCs. Thisanalyses
the crucial measurement was conducted
to identify the charge
using a pentiostat (Digi-IVY DY2300) (Neware, Shenzhen, China) at different
storage and charge transfer behaviors in the fabricated EDLCs. This measurement was scan rates, v asconducted
shown in
Figurea9.pentiostat
using The specific capacitance
(Digi-IVY from(Neware,
DY2300) CV analysis can be calculated
Shenzhen, China) atvia the following
different equation
scan rates, where
v as shown
the area of the CV curve, I (V) dV and the mass of active materials, m are involved [65].
in Figure 9. The specific capacitance from CV analysis can be calculated via the following equation The voltage
range for
where theCV measurement
area was between
of the CV curve, I(V) dV 0.0
andVthe
(V 1mass
) to 0.9
ofVactive
(V 2 ). materials, m are involved [65]. The
voltage range for CV measurement was between
Z V2 0.0 V (V1) to 0.9 V (V2).
I (V )dV
Cs = 𝑉2
𝐼(𝑉)𝑑𝑉 (16)
V1 2mv(V2 − V1 )
𝐶𝑠 = ∫ (16)
𝑉1 2𝑚𝑣(𝑉2 − 𝑉1 )

Figure 9. The plot of CV curves at different scan rates.

Figure 9. The plot of CV curves at different scan rates.
The CV curves in Figure 9 exhibit that as the scan rate increases, the shape of the curve changes
The CV curves
from rectangular in Figure
shape 9 exhibit
to a leaf-like that as
shape. the scan
These rateare
changes increases,
caused the shape
by the of the of
existence curve changes
the porosity
from rectangular shape to a leaf-like shape. These changes are caused by the existence
of the carbon electrodes and the internal resistance presents during the measurement [66]. The curves of the porosity
of thedepicted
also carbon electrodes
without anyandnoticeable
the internal resistance
peaks presents
that further during the
explained themeasurement
system did not [66]. The curves
undergo any
also depicted without any noticeable peaks that further explained the system did
reduction/oxidation reaction. The anions within the system will flow towards the positive electrode not undergo any
reduction/oxidation reaction.where
during the charging process The anions withinelectrode
the positive the systemwillwill flow
repel thetowards
cations sothethat
positive electrode
the cations will
during
attractsthe charging
to the process
negative whereThe
electrode. the positive electrode
electric field duringwillthis
repel the cations
process so that
embraces thethe cations and
electrode will
attracts to to
electrolyte thehold
negative electrode.
the electrons andThe electric
ions, field during
respectively this process
[67]. These processesembraces the electrode
are the explanation forand
the
electrolyte to hold the electrons and ions, respectively [67]. These processes are the
formation of double-layer charge to store the potential energy on the carbon electrodes surfaces [68]. explanation for
the formation
The calculated of double-layer
specific charge
capacitance, Cs to store
from CVthe potential
curves energy
analysis on the
is listed carbon
in Table 6 atelectrodes
various scansurfaces
rates.
[68]. The calculated specific capacitance, Cs from CV curves analysis is listed in Table 6 at various
scan rates.
Membranes 2020, 10, 389 13 of 20

Membranes 2020, 10, x FOR PEER REVIEW 13 of 21

Table 6. Specific capacitance, Cs of the EDLC at different scan rates.
Table 6. Specific capacitance, Cs of the EDLC at different scan rates.
Scan Rate (mV/s) Specific Capacitance (F/g)
Scan Rate
100 (mV/s) Specific Capacitance
4.18 (F/g)
100
50 4.18
8.46
20
50 17.15
8.46
10
20 24.46
17.15
10 24.46
The low Cs value at higher scan rate is because the energy loss is high at these scan rates due to the
The low Cs value at higher scan rate is because the energy loss is high at these scan rates due to
reduction of the amount of stored charges, which exhibits lower Cs value [69]. Further characterization
the reduction of the amount of stored charges, which exhibits lower Cs value [69]. Further
of the fabricated EDLC involved the charge–discharge profile, as shown in Figure 10, using the
characterization of the fabricated EDLC involved the charge–discharge profile, as shown in Figure
Galvanostatic technique by employing a Neware battery cycler. This profile is valuable to determine
10, using the Galvanostatic technique by employing a Neware battery cycler. This profile is valuable
the cyclic durability of the system as well as their capacitive behavior. The capacitive behaviour in
to determine the cyclic durability of the system as well as their capacitive behavior. The capacitive
the EDLC is comfirmed when the discharge slope is near to a straight line or linear curve [70]. As a
behaviour in the EDLC is comfirmed when the discharge slope is near to a straight line or linear curve
comparison to the Cs values from CV studies, the Cs values also can be calculated from the profile in
[70]. As a comparison to the Cs values from CV studies, the Cs values also can be calculated from the
Figure 10 by using the equation below and the obtained values are plotted in Figure 11.
profile in Figure 10 by using the equation below and the obtained values are plotted in Figure 11.
i𝑖
s 𝑠==
C𝐶 (17)
ms
𝑚𝑠

1.0

0.8 Vd
Potential (V)

0.6

0.4

0.2

0.0
0 100 200 300 400 500
Time (s)
Figure 10. Charge–discharge curves at the selected cycles.
Figure 10. cycles.

The
The calculated
calculated CsCs value
value for
for the
the first
first cycle
cycle is
is 39.68
39.68 F/g,
F/g, which
which isis slightly
slightly higher
higher than
than the
the values
values
obtained from CV analysis. This difference is reliable because both analyses display
obtained from CV analysis. This difference is reliable because both analyses display the capacitive the capacitive
properties
properties ofof the
the EDLC
EDLC [71].
[71]. At
At the
the 40th
40th cycle,
cycle, Cs
Cs value
value is
is increased
increased to to 50.34
50.34 F/g
F/g and
and then
then maintained
maintained
at
at an average of 48.19 F/g until the system completed the 100 cycles. The achievement based
an average of 48.19 F/g until the system completed the 100 cycles. The achievement based onon the
the
satisfactory specific capacitance values obtained by the EDLC, it can be concluded that
satisfactory specific capacitance values obtained by the EDLC, it can be concluded that the electrolytethe electrolyte in
this work
in this is suitable
work enough
is suitable to betoapplied
enough in theinelectrochemical
be applied the electrochemical devices applications.
devices Moreover,
applications. a tiny
Moreover,
voltage drop, V
a tiny voltage drop,
d is noticed in the charge–discharge profile as shown in Figure 10. The existence
Vd is noticed in the charge–discharge profile as shown in Figure 10. The existence of Vd
can
of Vbe attributed to the internal resistance within the system during the charge–discharge processes,
d can be attributed to the internal resistance within the system during the charge–discharge

processes, which also called as equivalent series resistance (ESR). The determination of this parameter
will involve the applied current, i of 1.5 mA and can be expressed as:
Membranes 2020, 10, 389 14 of 20

which also called as equivalent series resistance (ESR). The determination of this parameter will involve
Membranes 2020, 10, x FOR PEER REVIEW 14 of 21
the applied current, i of 1.5 mA and can be expressed as:
Membranes 2020, 10, x FOR PEER REVIEW 14 of 21

𝑉𝑑𝑟𝑜𝑝
V drop
𝐸𝑆𝑅== 𝑉𝑑𝑟𝑜𝑝
ESR (18) (18)
𝐸𝑆𝑅 = i𝑖 (18)
𝑖

80
80
(F/g)
(F/g)

60
60
capacitance
capacitance

40
40
Specific
Specific

20
20

0
0 0 20 40 60 80 100 120
0 20 40 60 80 100 120
Cycle number
Cycle number
Figure 11. Specific capacitance, Cs of the fabricated EDLC.
Figure
Figure 11.11. Specificcapacitance,
Specific capacitance, C Css of
ofthe
thefabricated
fabricatedEDLC.
EDLC.
The obtained ESR values for 100 cycles are illustrated in Figure 12, where 189.33 Ω is observed
The The
at the obtained
obtained
first ESR
cycle. ESR values
values
Throughout forfor
100100
the cycles
cycles
whole areillustrated
are illustrated
processes, the system in Figure
in Figure 12,
12,where
is noticed where 189.33Ω
189.33
to maintain ΩisESR
its isobserved
observed
at the at
at
the firstthe first
cycle.
range cycle. Throughout
Throughout
of 186.80 to 202.27 the
theΩ.whole whole processes,
processes,
This result showsthe the
system
that system
the EDLC is noticed
is noticed
has ato to maintain
maintain
small its ESR atatthe
its ESR internal
and constant therange
range of 186.80 to 202.27 Ω. This result shows that the EDLC has a small and constant internal
resistance
of 186.80 to 202.27 Ω. This
for 100 cyclesresult
which simplifies
shows the EDLC
that the electrostatic
has a process
small and between the internal
constant ions andresistance
charged for
resistance
electrode for 100 cycles which simplifies the electrostatic process between the ions and charged
[72].
100 cycles which simplifies the electrostatic process between the ions and charged electrode [72].
electrode [72].

400
400

300
300
(Ohm)
(Ohm)

200
200
ESR
ESR

100
100

0
0 0 20 40 60 80 100 120
0 20 40 60 80 100 120
Cycle number
Cycle number
Figure
Figure 12.12. Equivalentseries
Equivalent seriesresistance,
resistance, ESR
ESRofofthe
thefabricated EDLC.
fabricated EDLC.
Figure 12. Equivalent series resistance, ESR of the fabricated EDLC.
Membranes 2020, 10, 389 15 of 20
Membranes 2020, 10, x FOR PEER REVIEW 15 of 21

Figure1313
Figure depicts
depicts thethe calculated
calculated energy
energy andand power
power densities
densities of the
of the EDLC
EDLC for 100
for 100 cycles.
cycles. TheThevalues
values
are are determined
determined from thefrom the Equations
Equations (19) and(19) and
(20), where(20), the
where the operating
operating voltagevoltage
value, value, V, is
V, is included,
included,
which which
is at 0.9 V. is at 0.9 V.
2
E𝐸 = 𝐶C𝑠s𝑉V2
= 2 (19) (19)
2
2
𝑉V2
𝑃=
P = 4m(ESR) (20) (20)
4𝑚(𝐸𝑆𝑅)

12 800
Energy density (Wh/kg)

9 600

Power density (W/kg)

6 400

3 200

Energy density Power density

0 0
0 20 40 60 80 100 120

Cycle number
Figure13.
Figure 13. Energy density
densityand
andpower
powerdensity
densityofofthe fabricated
the EDLC.
fabricated EDLC.

Based
Basedon onFigure 13, the
Figure 13, theEDLC
EDLCinin this
this work
work achieved
achieved the energy
the energy densitydensity
of 4.46ofWh/kg
4.46 Wh/kg at the
at the first
first cycle.
cycle. Then,Then,
thethe energy
energy density
density is steadily
is steadily increased
increased to 5.66
to 5.66 Wh/kg
Wh/kg (40th
(40th cycle),
cycle), which
which remained
remained
around
around5.425.42Wh/kg
Wh/kguntil
untilthethecycle
cycle is completed.
completed.The Thepattern
patternofofenergy
energy density
density agrees
agrees with
with thethe specific
specific
capacitancetrend
capacitance trendin inFigure
Figure 11, 11, which
which described
describedthat thatthe
therequired
requiredamount
amount of of
energy
energyforfor
thethe
charge
charge
carriersinin
carriers eachcycle
each cycleofofthe
thecharge–discharge
charge–dischargeprocessprocessisisalmost
almostequivalent
equivalentin inorder
orderto tomove
movetowards
towards the
the electrodes
electrodes surfacessurfaces
[73]. On [73].
theOn the hand,
other other the
hand,
plotthe plot of density
of power power density
in Figurein13Figure
shows13a comparable
shows a
comparable
trend as the ESRtrend as the
plot. The ESR plot.ofThe
range rangedensity
power of power fordensity for the fabricated
the fabricated EDLC in EDLC in this
this work work
is between
is between
500.58 500.58
to 558.57 to 558.57
W/kg. W/kg. The almost-consistent
The almost-consistent values throughout
values throughout the 100
the 100 cycles cycles that
clarifies clarifies
ELDC
that ELDC possesses the capacitive characteristics [74]. This also means that the
possesses the capacitive characteristics [74]. This also means that the electrolyte consists of enormous electrolyte consists
of enormous
amount of free amount of free
ions, which ions, which
contributed to contributed
the formation to of
thea formation
double layerof a[75].
double layer
Lastly, [75].
the Lastly,
performance
the performance of EDLCs can be analyzed using the Columbic efficiency, 𝜂 where the stability of
of EDLCs can be analyzed using the Columbic efficiency, η where the stability of each cycle can be
each cycle can be revealed as plotted in Figure 14. This parameter involves the time of discharging, td
revealed as plotted in Figure 14. This parameter involves the time of discharging, td as well as charging,
as well as charging, tc, which can be expressed using the following equation:
tc , which can be expressed using the following equation:
𝑡𝑑
𝜂 = × 100 (21)
𝑡t
η = 𝑐d × 100 (21)
tc
The fabricated EDLC has a low efficiency of 57.89% at the first cycle. However, the performance
is found to enhanceEDLC
The fabricated for the next
has cycle
a low until the of
efficiency EDLC57.89%completed the cycle.
at the first 100 cycles where the
However, the performance
efficiency
values are consistent at an average of 92.88%. This result suggests that
is found to enhance for the next cycle until the EDLC completed the 100 cycles where the efficiency the system presents an
excellent performance in electrochemical devices with good contact of electrolyte–electrode
values are consistent at an average of 92.88%. This result suggests that the system presents an excellent because
the efficiency is above 90.0% [76].
performance in electrochemical devices with good contact of electrolyte–electrode because the efficiency
is above 90.0% [76].
 Membranes
Membranes 2020,
2020, 10, 10, 389
x FOR PEER REVIEW 16 of 20 16 of 21

120

90
Efficiency (%)

60

30

0
0 20 40 60 80 100 120
Cycle number
Figure
Figure 14.14.
TheThe
efficiency η of
efficiency 𝜂 ofthe
thefabricated EDLC.
fabricated EDLC.
4. Conclusions
4. Conclusions
The polymer electrolytes based on Dx:Cs:Mg(CH3 COO)2 :Ni with three different glycerol
The polymer have
concentration electrolytes based onThe
been well-prepared. Dx:Cs:Mg(CH
impedance study 3COO) :Ni with
has2verified thatthree differentwith
the electrolyte glycerol
42 wt.% of glycerol (A3) has the highest The
ionicimpedance of 7.71 ×
conductivity study −6
10 verified−1
S cm at room
concentration have been well-prepared. has that thetemperature.
electrolyte with
The ionic conductivity is found to be influenced by the transport parameters.
42 wt.% of glycerol (A3) has the highest ionic conductivity of 7.71 × 10 S cm at room temperature.
−6 The understanding
−1 from
dielectric analysis revealed that the electrolytes in this system obeyed the non-Debye behavior. The A3
The ionic conductivity is found to be influenced by the transport parameters. The understanding
electrolyte exhibited a dominancy of ions (tion > te ) with a breakdown voltage of 2.08 V. The fabricated
from dielectric analysis revealed that the electrolytes in this system obeyed the non-Debye behavior.
EDLC achieved the specific capacitance values of 24.46 F/g and 39.68 F/g via CV curve and the
The A3charge–discharge
electrolyte exhibited a dominancy of ions (t ion > te) with a breakdown voltage of 2.08 V. The
profile, respectively. The other significant parameters to evaluate the performance
fabricated EDLC achieved the specificsuch
of EDLC have been determined, capacitance
as internalvalues of 24.46
resistance F/gtoand
(186.80 39.68
202.27 Ω),F/g via CV
energy curve and
density
the charge–discharge
(4.46 Wh/kg), powerprofile, respectively.
density (500.58 The and
to 558.57 W/kg) other significant
efficiency (92.88%).parameters
These resultstoimply
evaluate
that the
the system
performance presents
of EDLC an excellent
have performance such
been determined, in some
as electrochemical devices
internal resistance with a to
(186.80 good contact
202.27 Ω),ofenergy
electrolyte–electrode because the efficiency is above 90.0%.
density (4.46 Wh/kg), power density (500.58 to 558.57 W/kg) and efficiency (92.88%). These results
imply that
AuthortheContributions:
system presents an excellentS.B.A.,
Conceptualization, performance in some
S.R.S., Y.M.Y. electrochemical
and M.F.Z.K.; devices
Formal analysis, with a good
A.S.F.M.A.;
Investigation, R.T.A.; Methodology, S.B.A.; Project administration,
contact of electrolyte–electrode because the efficiency is above 90.0%. S.B.A., S.R.S., S.A.-Z. and M.F.Z.K.;
Supervision, S.B.A.; Validation, A.S.F.M.A., Y.M.Y., R.T.A. and W.O.K.; Writing—original draft, A.S.F.M.A.;
Writing—review & editing, S.B.A., S.R.S., Y.M.Y., R.T.A., S.A.-Z., W.O.K. and M.F.Z.K. All authors have read and
Authoragreed
Contributions: Conceptualization,
to the published S.B.A., S.R.S., Y.M.Y. and M.F.Z.K.; Formal analysis, A.S.F.M.A.;
version of the manuscript.
Investigation,
Funding:R.T.A.; Methodology,
This research S.B.A.; funding.
received no external Project administration, S.B.A., S.R.S., S.A.-Z. and M.F.Z.K.;
Supervision, S.B.A.; Validation,
Acknowledgments: A.S.F.M.A.,
The authors Y.M.Y.,
appreciatively R.T.A. the
acknowledge andfinancial
W.O.K.; Writing—original
support for this work by draft, A.S.F.M.A.;
the Ministry
Writing—review & editing,
of Higher Education S.B.A., S.R.S.,
& Scientific Y.M.Y., R.T.A.,
Research-Kurdish S.A.-Z.,
National W.O.K.
Research and(KNRC),
Council M.F.Z.K. All authors
Kurdistan have read
Regional
Government-Iraq. The financial support by the
and agreed to the published version of the manuscript. University of Sulaimani and Komar Research Center (KRC) and
Komar University of Science and Technology is sincerely appreciated.
Funding: This research
Conflicts received
of Interest: no external
The authors funding.
declare no conflict of interest.

Acknowledgments: The authors appreciatively acknowledge the financial support for this work by the Ministry
of Higher Education & Scientific Research-Kurdish National Research Council (KNRC), Kurdistan Regional
Government-Iraq. The financial support by the University of Sulaimani and Komar Research Center (KRC) and
Komar University of Science and Technology is sincerely appreciated.

Conflicts of Interest: The authors declare no conflict of interest.

Membranes 2020, 10, 389 17 of 20

References
1. Bella, F.; Lamberti, A.; Scalia, A.; Bianco, S.; Tresso, E.; Pirri, C.F.; Gerbaldi, C. A flexible and portable
powerpack by solid-state supercapacitor and dye-sensitized solar cell integration. J. Power Sources 2017, 359,
311–321. [CrossRef]
2. Tooming, T.; Thomberg, T.; Kurig, H.; Jänes, A.; Lust, E. High power density supercapacitors based
on the carbon dioxide activated d-glucose derived carbon electrodes and 1-ethyl-3-methylimidazolium
tetrafluoroborate ionic liquid. J. Power Sources 2015, 280, 667–677. [CrossRef]
3. Inagaki, M.; Konno, H.; Tanaike, O. Carbon materials for electrochemical capacitors. J. Power Sources 2010,
195, 7880–7903. [CrossRef]
4. Zhang, D.; Zhang, X.; Chen, Y.; Yu, P.; Wang, C.; Ma, Y. Enhanced capacitance and rate capability of
graphene/polypyrrole composite as electrode material for supercapacitors. J. Power Sources 2011, 196,
5990–5996. [CrossRef]
5. Pell, W.G.; Conway, B.E. Peculiarities and requirements of asymmetric capacitor devices based on combination
of capacitor and battery-type electrodes. J. Power Sources 2004, 136, 334–345. [CrossRef]
6. Wang, H.; Lin, J.; Shen, Z.X. Polyaniline (PANi) based electrode materials for energy storage and conversion.
J. Sci. Adv. Mater. Devices 2016, 1, 225–255. [CrossRef]
7. Vettori, M.H.P.B.; Franchetti, S.M.M.; Contiero, J. Structural characterization of a new dextran with a low
degree of branching produced by Leuconostoc mesenteroides FT045B dextransucrase. Carbohydr. Polym.
2012, 88, 1440–1444. [CrossRef]
8. Siddiqui, N.N.; Aman, A.; Silipo, A.; Qader, S.A.U.; Molinaro, A. Structural analysis and characterization of
dextran produced by wild and mutant strains of Leuconostoc mesenteroides. Carbohydr. Polym. 2014, 99,
331–338. [CrossRef]
9. Aziz, S.B.; Hamsan, M.H.; Kadir, M.F.Z.; Karim, W.O.; Abdullah, R.M. Development of polymer blend
electrolyte membranes based on chitosan: Dextran with high ion transport properties for EDLC application.
Int. J. Mol. Sci. 2019, 20, 1–26. [CrossRef]
10. Sarwat, F.; Ahmed, N.; Aman, A.; Qader, S.A.U. Optimization of growth conditions for the isolation of
dextran producing Leuconostoc spp. from indigenous food sources. Pak. J. Pharm. Sci. 2013, 26, 793–797.
[PubMed]
11. Aziz, S.B.; Hamsan, M.H.; Kadir, M.F.Z.; Woo, H.J. Design of Polymer Blends Based on Chitosan:
POZ with Improved Dielectric Constant for Application in Polymer Electrolytes and Flexible Electronics.
Adv. Polym. Technol. 2020, 2020, 1–10. [CrossRef]
12. Stepniak, I.; Galinski, M.; Nowacki, K.; Wysokowski, M.; Jakubowska, P.; Bazhenov, V.V.; Leisegang, T.;
Ehrlich, H.; Jesionowski, T. A novel chitosan/sponge chitin origin material as a membrane for
supercapacitors-preparation and characterization. RSC Adv. 2016, 6, 4007–4013. [CrossRef]
13. Zulkifli, A.M.; Said, N.I.A.M.; Aziz, S.B.; Hisham, S.; Shah, S.; Bakar, A.A.; Abidin, Z.H.Z.; Tajuddin, H.A.;
Sulaiman, L.; Brza, M.A.; et al. Electrochemical characteristics of phthaloyl chitosan based gel polymer
electrolyte for dye sensitized solar cell application. Int. J. Electrochem. Sci. 2020, 15, 7434–7447. [CrossRef]
14. Khiar, A.S.A.; Puteh, R.; Arof, A.K. Characterizations of chitosan-ammonium triflate (NH 4CF 3so 3)
complexes by FTIR and impedance spectroscopy. Phys. Status Solidi Appl. Mater. Sci. 2006, 203, 534–543.
[CrossRef]
15. Dueramae, I.; Okhawilai, M.; Kasemsiri, P.; Uyama, H.; Kita, R. Properties enhancement of carboxymethyl
cellulose with thermo-responsive polymer as solid polymer electrolyte for zinc ion battery. Sci. Rep. 2020,
10, 1–12. [CrossRef]
16. Moniha, V.; Alagar, M.; Selvasekarapandian, S.; Sundaresan, B.; Boopathi, G. Conductive bio-polymer
electrolyte iota-carrageenan with ammonium nitrate for application in electrochemical devices. J. Non.
Cryst. Solids 2018, 481, 424–434. [CrossRef]
17. Parameswaran, V.; Nallamuthu, N.; Devendran, P.; Nagarajan, E.R.; Manikandan, A. Electrical conductivity
studies on Ammonium bromide incorporated with Zwitterionic polymer blend electrolyte for battery
application. Phys. B Condens. Matter 2017, 515, 89–98. [CrossRef]
18. Bakar, N.Y.A.; Muhamaruesa, N.H.M.; Aniskari, N.A.B.; Isa, M.I.N.M. Electrical Studies of Carboxy
Methycellulose-Chitosan Blend Biopolymer Doped Dodecyltrimethyl Ammonium Bromide Solid Electrolytes.
Am. J. Appl. Sci. 2015, 12, 40–46. [CrossRef]
Membranes 2020, 10, 389 18 of 20

19. Gong, S.D.; Huang, Y.; Cao, H.J.; Lin, Y.H.; Li, Y.; Tang, S.H.; Wang, M.S.; Li, X. A green and
environment-friendly gel polymer electrolyte with higher performances based on the natural matrix
of lignin. J. Power Sources 2016, 307, 624–633. [CrossRef]
20. Yusof, Y.M.; Shukur, M.F.; Illias, H.A.; Kadir, M.F.Z. Conductivity and electrical properties of corn
starch-chitosan blend biopolymer electrolyte incorporated with ammonium iodide. Phys. Scr. 2014,
89, 1–10. [CrossRef]
21. Zainol, N.H.; Osman, Z.; Othman, L.; Md. Isa, K.B. Transport and Morphological Properties of Gel Polymer
Electrolytes Containing Mg(CF3 SO3 )2 . Adv. Mater. Res. 2013, 686, 137–144. [CrossRef]
22. Syahidah, S.N.; Majid, S.R. Ionic liquid-based polymer gel electrolytes for symmetrical solid-state electrical
double layer capacitor operated at different operating voltages. Electrochim. Acta 2015, 175, 184–192. [CrossRef]
23. Liang, S.; Huang, Q.; Liu, L.; Yam, K.I. Microstructure and molecular interaction in glycerol plasticized
chitosan/poly(vinyl alcohol) blending films. Macromol. Chem. Phys. 2009, 210, 832–839. [CrossRef]
24. Shukur, M.F.; Hamsan, M.H.; Kadir, M.F.Z. Investigation of plasticized ionic conductor based on chitosan
and ammonium bromide for EDLC application. Mater. Today Proc. 2019, 17, 490–498. [CrossRef]
25. Asnawi, A.S.F.M.; Aziz, S.B.; Nofal, M.; Abdulwahid, R.T.; Kadir, M.F.Z.; Hamsan, M.H.; Brza, M.A.;
Yusof, Y.M.; Abdilwahid, R.T. Glycerolized Li + Ion Conducting Chitosan-Based Polymer Electrolyte for
Energy Storage EDLC Device Applications with Relatively High Energy Density. Polymers 2020, 12, 1433.
[CrossRef]
26. Hamsan, H.M.; Aziz, S.; Kadir, M.F.Z.; Brza, M.A.; Karim, W. The study of EDLC device fabricated from
plasticized magnesium ion conducting chitosan based polymer electrolyte. Polym. Test. 2020, 106714. [CrossRef]
27. Yusof, Y.M.; Kadir, M.F.Z. Electrochemical characterizations and the effect of glycerol in biopolymer
electrolytes based on methylcellulose-potato starch blend. Mol. Cryst. Liq. Cryst. 2016, 627, 220–233.
[CrossRef]
28. Kadir, M.; Salleh, N.; Hamsan, M.; Aspanut, Z.; Majid, N.; Shukur, M. Biopolymeric electrolyte based on
glycerolized methyl cellulose with NH4Br as proton source and potential application in EDLC. Ionics 2018,
24, 1651–1662. [CrossRef]
29. Brza, M.A.; Aziz, S.B.; Anuar, H.; Al Hazza, M.H.F. From green remediation to polymer hybrid fabrication
with improved optical band gaps. Int. J. Mol. Sci. 2019, 20, 3910. [CrossRef]
30. Asnawi, A.S.F.M.; Aziz, S.B.; Nofal, M.M.; Yusof, Y.M.; Brevik, I. Metal Complex as a Novel Approach to
Enhance the Amorphous Phase and Improve the EDLC Performance of Plasticized Proton Conducting
Chitosan-Based Polymer Electrolyte. Membranes 2020, 10, 132. [CrossRef]
31. Kadir, M.; Hamsan, M. Green electrolytes based on dextran-chitosan blend and the effect of NH4SCN as
proton provider on the electrical response studies. Ionics 2018, 24, 2379–2398. [CrossRef]
32. Mazuki, N.F.; Abdul Majeed, A.P.P.; Nagao, Y.; Samsudin, A.S. Studies on ionics conduction properties
of modification CMC-PVA based polymer blend electrolytes via impedance approach. Polym. Test. 2020,
81, 106234. [CrossRef]
33. Gohel, K.; Kanchan, D.K. Ionic conductivity and relaxation studies in PVDF-HFP:PMMA-based gel polymer
blend electrolyte with LiClO 4 salt. J. Adv. Dielectr. 2018, 8, 1850005. [CrossRef]
34. Misenan, M.; Khiar, A. Conductivity, Dielectric And Modulus Studies of Methylcellulose-NH 4 TF Polymer.
Eurasian J. Biol. Chem. Sci. J. 2018, 1, 59–62.
35. Ramya, C.S.; Selvasekarapandian, S.; Savitha, T.; Hirankumar, G.; Baskaran, R.; Bhuvaneswari, M.S.;
Angelo, P.C. Conductivity and thermal behavior of proton conducting polymer electrolyte based on poly
(N-vinyl pyrrolidone). Eur. Polym. J. 2006, 42, 2672–2677. [CrossRef]
36. Teo, L.P.; Buraidah, M.H.; Nor, A.F.M.; Majid, S.R. Conductivity and dielectric studies of Li2 SnO3 . Ionics 2012,
18, 655–665. [CrossRef]
37. Aziz, S.B.; Marif, R.B.; Brza, M.A.; Hamsan, M.H.; Kadir, M.F.Z. Employing of Trukhan model to estimate ion
transport parameters in PVA based solid polymer electrolyte. Polymers 2019, 11, 1694. [CrossRef]
38. Abarna, S.; Hirankumar, G. Electrical, dielectric and electrochemical studies on new Li ion conducting solid
polymer electrolytes based on polyethylene glycol p-tert-octylphenyl ether. Polym. Sci. Ser. A 2017, 59,
660–668. [CrossRef]
39. Guan, K.H.; Farhana, N.K.; Omar, F.S.; Saidi, N.M.; Bashir, S.; Ramesh, S.; Ramesh, K. Influence of
tetraglyme towards magnesium salt dissociation in solid polymer electrolyte for electric double layer
capacitor. J. Polym. Res. 2020, 27, 1–9. [CrossRef]
Membranes 2020, 10, 389 19 of 20

40. Lee, D.K.; Allcock, H.R. The effects of cations and anions on the ionic conductivity of
poly[bis(2-(2-methoxyethoxy)ethoxy)phosphazene] doped with lithium and magnesium salts of
trifluoromethanesulfonate and bis(trifluoromethanesulfonyl)imidate. Solid State Ionics 2010, 181, 1721–1726.
[CrossRef]
41. Sengwa, R.J.; Dhatarwal, P. Predominantly chain segmental relaxation dependent ionic conductivity of
multiphase semicrystalline PVDF/PEO/LiClO4 solid polymer electrolytes. Electrochim. Acta 2020, 338, 135890.
[CrossRef]
42. Yahya, M.Z.A.; Arof, A.K. Effect of oleic acid plasticizer on chitosan-lithium acetate solid polymer electrolytes.
Eur. Polym. J. 2003, 39, 897–902. [CrossRef]
43. Mohamed, A.S.; Shukur, M.F.; Kadir, M.F.Z.; Yusof, Y.M. Ion conduction in chitosan-starch blend based
polymer electrolyte with ammonium thiocyanate as charge provider. J. Polym. Res. 2020, 27. [CrossRef]
44. Rani, M.S.A.; Ahmad, A.; Mohamed, N.S. A comprehensive investigation on electrical characterization and
ionic transport properties of cellulose derivative from kenaf fibre-based biopolymer electrolytes. Polym. Bull.
2018, 75, 5061–5074. [CrossRef]
45. Asnawi, A.; Azli, A.; Hamsan, M.; Kadir, M.; Yusof, Y. Electrical And Infrared Spectroscopic Analysis Of
Solid Polymer Electrolyte Based On Polyethylene Oxide And Graphene Oxide Blend. Malaysian J. Anal. Sci.
2020, 24, 682–697.
46. Ramly, K.; Isa, M.I.N.; Khiar, A.S.A. Conductivity and dielectric behaviour studies of starch/PEO+ x wt-%NH
4 NO 3 polymer electrolyte. Mater. Res. Innov. 2011, 15, s82–s85. [CrossRef]
47. Aziz, S.B.; Abdullah, R.M.; Kadir, M.F.Z.; Ahmed, H.M. Non suitability of silver ion conducting polymer
electrolytes based on chitosan mediated by barium titanate (BaTiO3) for electrochemical device applications.
Electrochim. Acta 2019, 296, 494–507. [CrossRef]
48. Pawlicka, A.; Tavares, F.C.; Dörr, D.S.; Cholant, C.M.; Ely, F.; Santos, M.J.L.; Avellaneda, C.O. Dielectric
behavior and FTIR studies of xanthan gum-based solid polymer electrolytes. Electrochim. Acta 2019, 305,
232–239. [CrossRef]
49. Aziz, S.B.; Abdullah, R.M. Crystalline and amorphous phase identification from the tanδ relaxation peaks and
impedance plots in polymer blend electrolytes based on [CS:AgNt]x:PEO(x−1) (10 ≤ x ≤ 50). Electrochim. Acta
2018, 285, 30–46. [CrossRef]
50. Idris, N.H.; Senin, H.B.; Arof, A.K. Dielectric spectra of LiTFSI-doped chitosan/PEO blends. Ionics 2007, 13,
213–217. [CrossRef]
51. Fuzlin, A.F.; Rasali, N.M.J.; Samsudin, A.S. Effect on Ammonium Bromide in dielectric behavior based
Alginate Solid Biopolymer electrolytes. IOP Conf. Ser. Mater. Sci. Eng. 2018, 342, 1–8. [CrossRef]
52. Arof, A.K.; Amirudin, S.; Yusof, S.Z.; Noor, I.M. A method based on impedance spectroscopy to determine
transport properties of polymer electrolytes. Phys. Chem. Chem. Phys. 2014, 16, 1856–1867. [CrossRef]
[PubMed]
53. Fadzallah, I.A.; Noor, I.M.; Careem, M.A.; Arof, A.K. Investigation of transport properties of chitosan-based
electrolytes utilizing impedance spectroscopy. Ionics 2016, 22, 1635–1645. [CrossRef]
54. Yusof, Y.M.; Shukur, M.F.; Hamsan, M.H.; Jumbri, K.; Kadir, M.F.Z. Plasticized solid polymer electrolyte
based on natural polymer blend incorporated with lithium perchlorate for electrical double-layer capacitor
fabrication. Ionics 2019, 25, 5473–5484. [CrossRef]
55. Pritam; Arya, A.; Sharma, A.L. Dielectric relaxations and transport properties parameter analysis of novel
blended solid polymer electrolyte for sodium-ion rechargeable batteries. J. Mater. Sci. 2019, 54, 7131–7155.
[CrossRef]
56. Shukur, M.F.; Ithnin, R.; Kadir, M.F.Z. Ionic conductivity and dielectric properties of potato starch-magnesium
acetate biopolymer electrolytes: The effect of glycerol and 1-butyl-3-methylimidazolium chloride. Ionics 2016,
22, 1113–1123. [CrossRef]
57. Chai, M.N.; Isa, M.I.N. Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl
Cellulose Doped with Oleic Acid and Plasticized with Glycerol. Sci. Rep. 2016, 6, 1–7. [CrossRef]
58. Rani, M.S.A.; Ahmad, A.; Mohamed, N.S. Influence of nano-sized fumed silica on physicochemical and
electrochemical properties of cellulose derivatives-ionic liquid biopolymer electrolytes. Ionics 2018, 24,
807–814. [CrossRef]
59. Shukur, M.F.; Ithnin, R.; Kadir, M.F.Z. Protonic Transport Analysis of Starch-Chitosan Blend Based Electrolytes
and Application in Electrochemical Device. Mol. Cryst. Liq. Cryst. 2014, 603, 52–65. [CrossRef]
 Membranes 2020, 10, 389 20 of 20

60. Rama Mohan, K.; Achari, V.B.S.; Rao, V.V.R.N.; Sharma, A.K. Electrical and optical properties of (PEMA/PVC)
polymer blend electrolyte doped with NaClO4. Polym. Test. 2011, 30, 881–886. [CrossRef]
61. Francis, K.A.; Liew, C.W.; Ramesh, S.; Ramesh, K.; Ramesh, S. Ionic liquid enhanced magnesium-based
polymer electrolytes for electrical double-layer capacitors. Ionics 2016, 22, 919–925. [CrossRef]
62. Sampathkumar, L.; Christopher Selvin, P.; Selvasekarapandian, S.; Perumal, P.; Chitra, R.; Muthukrishnan, M.
Synthesis and characterization of biopolymer electrolyte based on tamarind seed polysaccharide,
lithium perchlorate and ethylene carbonate for electrochemical applications. Ionics 2019, 25, 1067–1082.
[CrossRef]
63. Aziz, S.B.; Hadi, J.M.; Elham, E.M.; Abdulwahid, R.T.; Saeed, S.R.; Marf, A.S.; Karim, W.O.; Kadir, M.F.Z.
The study of plasticized amorphous biopolymer blend electrolytes based on polyvinyl alcohol (PVA):
Chitosan with high ion conductivity for energy storage electrical double-layer capacitors (EDLC) device
application. Polymers 2020, 12, 1938. [CrossRef] [PubMed]
64. Shuhaimi, N.E.A.; Alias, N.A.; Majid, S.R.; Arof, A.K. Electrical Double Layer Capacitor with Proton
Conducting K-Carrageenan–Chitosan Electrolytes. Funct. Mater. Lett. 2009, 1, 195–201. [CrossRef]
65. Lee, J.S.M.; Briggs, M.E.; Hu, C.C.; Cooper, A.I. Controlling electric double-layer capacitance and
pseudocapacitance in heteroatom-doped carbons derived from hypercrosslinked microporous polymers.
Nano Energy 2018, 46, 277–289. [CrossRef]
66. Bandaranayake, C.M.; Weerasinghe, W.A.D.S.S.; Vidanapathirana, K.P.; Perera, K.S. A Cyclic Voltammetry
study of a gel polymer electrolyte based redox-capacitor. Sri Lankan J. Phys. 2016, 16, 19–27. [CrossRef]
67. Kadir, M.F.Z.; Arof, A.K. Application of PVA-chitosan blend polymer electrolyte membrane in electrical
double layer capacitor. Mater. Res. Innov. 2013, 15, S217–S220. [CrossRef]
68. Fattah, N.F.A.; Ng, H.M.; Mahipal, Y.K.; Numan, A.; Ramesh, S.; Ramesh, K. An approach to solid-state
electrical double layer capacitors fabricated with graphene oxide-doped, ionic liquid-based solid copolymer
electrolytes. Materials 2016, 9, 450. [CrossRef]
69. Muchakayala, R.; Song, S.; Wang, J.; Fan, Y.; Bengeppagari, M.; Chen, J.; Tan, M. Development and
supercapacitor application of ionic liquid-incorporated gel polymer electrolyte films. J. Ind. Eng. Chem. 2018,
59, 79–89. [CrossRef]
70. Aziz, S.B.; Hamsan, M.H.; Abdullah, R.M.; Kadir, M.F.Z. A promising polymer blend electrolytes based
on chitosan: Methyl cellulose for EDLC application with high specific capacitance and energy density.
Molecules 2019, 24, 2503. [CrossRef]
71. Yusof, Y.M.; Majid, N.A.; Kasmani, R.M.; Illias, H.A.; Kadir, M.F.Z. The Effect of Plasticization on Conductivity
and Other Properties of Starch/Chitosan Blend Biopolymer Electrolyte Incorporated with Ammonium Iodide.
Mol. Cryst. Liq. Cryst. 2014, 603, 73–88. [CrossRef]
72. Kwon, Y.H.; Kumar, S.; Bae, J.; Seo, Y. CVD-graphene for low equivalent series resistance in
rGO/CVD-graphene/Ni-based supercapacitors. Nanotechnology 2018, 29. [CrossRef] [PubMed]
73. Shukur, M.F.; Ithnin, R.; Kadir, M.F.Z. Electrical characterization of corn starch-LiOAc electrolytes and
application in electrochemical double layer capacitor. Electrochim. Acta 2014, 136, 204–216. [CrossRef]
74. Mazuki, N.; Abdul Majeed, A.P.P.; Samsudin, A.S. Study on electrochemical properties of CMC-PVA doped
NH4Br based solid polymer electrolytes system as application for EDLC. J. Polym. Res. 2020, 27, 1–13.
[CrossRef]
75. Aziz, S.B.; Hamsan, M.H.; Brza, M.A.; Kadir, M.F.Z.; Muzakir, S.K.; Abdulwahid, R.T. Effect of glycerol on
EDLC characteristics of chitosan:methylcellulose polymer blend electrolytes. J. Mater. Res. Technol. 2020, 9,
8355–8366. [CrossRef]
76. Lim, C.S.; Teoh, K.H.; Liew, C.W.; Ramesh, S. Capacitive behavior studies on electrical double layer
capacitor using poly (vinyl alcohol)-lithium perchlorate based polymer electrolyte incorporated with TiO2.
Mater. Chem. Phys. 2014, 143, 661–667. [CrossRef]

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