j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/jmrt

Original Article

Design of potassium ion conducting PVA based

polymer electrolyte with improved ion transport
properties for EDLC device application

Shujahadeen B. Aziz a,b,*, Ahmad S.F.M. Asnawi c,

Rebar T. Abdulwahid a,d, Hewa O. Ghareeb e, Saad M. Alshehri f,
Tansir Ahamad f, Jihad M. Hadi g, M.F.Z. Kadir h
a
Hameed Majid Advanced Polymeric Materials Research Lab., Physics Department, College of Science, University of
Sulaimani, Qlyasan Street, Kurdistan Regional Government, Sulaimani, 46001, Iraq
b
Department of Civil Engineering, College of Engineering, Komar University of Science and Technology, Kurdistan
Regional Government, Sulaimani, 46001, Iraq
c
Chemical Engineering Section, Universiti Kuala Lumpur Malaysian Institute of Chemical & Bioengineering
Technology (UniKL MICET), Alor Gajah, Malacca, 78000, Malaysia
d
Department of Physics, College of Education, University of Sulaimani, Old Campus, Kurdistan Regional
Government, Sulaimani, Iraq
e
Department of Chemistry, College of Science, University of Sulaimani, Qlyasan Street, Kurdistan Regional
Government, Sulaimani, 46001, Iraq
f
Department of Chemistry, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia
g
Department of Medical Laboratory of Science, College of Health Sciences, University of Human Development,
Kurdistan Regional Government, Iraq
h
Centre for Foundation Studies in Science, University of Malaya, Kuala Lumpur, 50603, Malaysia

article info abstract

Article history: This work presents a report on the preparation of plasticized polyvinyl alcohol PVA-
Received 13 February 2021 based polymer electrolytes using solution cast technique and their characteristics
Accepted 16 May 2021 using a number of electrochemical techniques. Electrical impedance spectroscopy (EIS),
Available online 24 May 2021 linear sweep voltammetry (LSV), and transfer number measurement (TNM) techniques
were examined on the prepared films to determine the conductivity, decomposition
Keywords: voltage and ion transference number, respectively. The cyclic voltammetry (CV) and
Plasticized electrolyte charge-discharging measurements were implemented on an assembled EDLC device to
PVA estimate the charge storage process and evaluate the device performance, respectively.
Potassium iodide (KI) The EIS was employed for measuring the direct current (DC) electrical conductivity of the
EEC modeling films and calculating the ion transport parameters. The CV and charge-discharging re-
Transport properties sponses were used to estimate the capacitance and stability, respectively. The influence
EDLC device of plasticization on the polymer electrolytes was investigated in terms of electro-
chemical properties. The TNM measurements were used to determine te and tion
respectively. The obtained ionic transference number, tion for the electrolytes incorpo-
rated with 40 wt.% and 50 wt.% of glycerol content were found to be 0.969 and 0.944,

* Corresponding author.
E-mail address: shujahadeenaziz@gmail.com (S.B. Aziz).
https://doi.org/10.1016/j.jmrt.2021.05.017
2238-7854/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://
creativecommons.org/licenses/by/4.0/).
934 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6

respectively. The LSV study was used to identify the decomposition voltage of the
sample. The absence of redox peaks was proved via CV technique, indicating the
mechanism of the charge storing process that comprised ion accumulation at the
interfacial region. The initial specific capacitance (Cs) of the fabricated EDLC displayed
the value of 152.4 F/g.
© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY license (http://creativecommons.org/licenses/by/4.0/).

methodologies, such as the incorporation of plasticizer,

1. Introduction
Polymer electrolytes are among the attracting solid-state
coordinating materials for ionic conduction in solid and
flexible membranes [1e4]. The solid polymer electrolyte
(SPE) can be considered as a good alternative to the tradi-
tional organic solegel electrolytes have been recognized and
studied extensively. These categories of materials are char-
acterized by dimensional stability, ease of processability and
handling, flexibility, relatively wide potential window, and to
the large extent environmentally friendly [5,6]. Furthermore,
these materials are superior over liquid electrolytes in terms
of mechanical properties, convenient film formation,
appropriate size, and compatibility with the electrode [7,8].
Investigation of SPEs as novel materials with preferred
properties has been devoted during the 1970s. Wright and
co-workers are pioneers in this field in which the work is
addressed towards examining ionic conducting polymer-
salt mixtures. Armand and co-workers have been also
interested in polymer-salt complexes [9,10].
As stated previously, these electrolytes have capability to
form thin films that are utilized in a number of applications.
There are several environmental waste problems including
non-biodegradable and petroleum-based plastic packaging
films that encourage researchers to think about alternatives.
The potential alternatives will be those that possess
renewable natural biopolymer-based film ability. These
electrolytes are also characterized by non-toxicity and bio-
compatibility. The polarity of the electrolytes due to the
existence of oxygen encourages the produced films to be
tightly packed, ordered hydrogen-bonded network structure
[11e13]. All these make a synthetic biopolymer like poly
(vinyl alcohol) (PVA) the material of choice. Additionally, it
possesses a relatively high dielectric strength, plausible
charge storage capacity. It is worth-mentioning that the
electrical and optical properties are depending on the nature
of dopant. Based on structure perspective, PVA enriches in
hydroxyl groups attached to methane carbons in the chain
backbone. The functional group allows PVA to form
hydrogen bonding with components of proper dopant [14].
Furthermore, the most common favorable properties of PVA
are polarity, reasonable thermo-stability, chemical resis-
tance, ease of processability, and transparency [15,16]. The
other superior properties of PVA are non-toxicity, water-
solubility, high crystallinity, biodegradability, and biocom-
patibility [17]. The only obvious drawback of PVA is the
conductivity that can be improved via several
nano-filler, and polymer blending [18,19].
Literature has shown a wide range of dopant salts which
have been used during the preparation of polymer electro-
lytes. Potassium iodide (KI) is among the frequently used salts
for the polymer electrolytes, which has suitable lattice energy
of 632 kJ/mol [20]. It is well-known that the lattice energy of
salts can substantial impact on the conductivity performance
of the polymer electrolytes [21,22]. Salts with high lattice en-
ergy lacks ease dissociation process; whereas, ions re-
association is very common in low lattice energy salts. Both
cases result in lower free ions availability, which in turn drops
the ionic conductivity of the polymer electrolyte [22,23]. Thus,
one need to carefully select the dopant salt during the polymer
electrolyte preparation. The lattice energy of KI (632 kJ/mol) is
considered to be in a suitable range, and can be successfully
employed in the polymer electrolyte preparation [20].
Another fundamental approach for boosting the con-
ductivity of polymer electrolytes is through the introduction
of plasticizers [24e27]. Various types of plasticizers have
been used to enhance the structural and electrical properties
of the polymer electrolytes such as glycerol, ethylene car-
bonate (EC) and polyethylene glycol (PEG) [24e27]. Glycerol
was found to significantly improve the overall conductivity
of the polymer electrolyte, due to the existing multi hydroxyl
(OH) functional groups which can dissociate more salt,
consequently more free ion will be available for conduction
[25e27]. Additionally, the OH functional groups of glycerol
can destroy the inter and intra-hydrogen bonding that exists
in the polymer matrix, which increase the amorphous pha-
ses that are essential for the ion transport process [25e27].
Therefore, in the current study, for the conductivity
enhancement of the PVA host polymer electrolyte both KI
and glycerol will be selected as the dopant salt and plasti-
cizer, respectively.
Polymer electrolytes make a breakthrough when utilized
in energy storage devices, for example, electrochemical
double-layer capacitors (EDLCs) which can be a suitable
choice in various applications. These devices possess a long
life cycle, cost-effective fabrication, safety, and high per-
formance [28,29]. For these reasons, many research groups
have focused on developing renewable energy devices, such
as supercapacitors (SCs) or so-called ultracapacitors. The
SCs are characterized by large power density, speedy
charging time, excellent cyclability, and inexpensive fabri-
cation [30e32]. It is important to mention that the SCs
comprise EDLCs, pseudocapacitors, and hybrid capacitors.
Nowadays, EDLCs appear as a potential alternative for
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6
conventional batteries. In EDLCs, the energy storage mech-
anism relies on the non-Faradaic process, i.e., establishing
double-layer ions on the carbon-based electrodes are
responsible for energy storage [33e35]. In this work, the
main focus is to study the effect of different glycerol con-
centration on PVAeKI complex electrolyte conductivity and
other electrochemical data. The highest conducting elec-
trolyte was applied in the EDLC and analyzed its breakdown
voltage as well as the specific capacitance.
2. Experimental
2.1. Plasticized polymer electrolyte (PPE) preparation
The PVA (Mw 9000e10,000, 80% hydrolyzed) was bought from
SigmaeAldrich and used without further purification. PVA
solution was prepared by dissolving 1 g of PVA in 40 mL

2.5.
distilled water under stirring with a magnetic stirrer at 85 C
for 65 min and then cooled to room temperature. A constant
weight percent (40 wt. %) of potassium iodide KI (Sigma-
eAldrich, Mw 166.00, 99%) salt was added to the solutions of
PVA and mixed with a magnetic stirrer at ambient tempera-
ture till KI in the solutions was dissolved. Lastly, PVA:KI were
plasticized with 10, 20, 30, 40, and 50 wt.% glycerol (Sigma-
eAldrich, Mw 92.09, 99%), and were coded as PVKI1, PVKI2,
PVKI3, PVKI4, and PVKI5, respectively. The whole solution was
stirred further to get a homogeneous solution and then kept at
room temperature in the plastic Petri dish for drying. Prior to
characterization and the EDLC device preparation, the sam-
ples were further dried with blue silica gels.
2.2. Electrochemical impedance spectroscopy (EIS)
The impedance data of plasticized PVA based electrolyte films
were taken using EIS [3532-50 LCR Hi TESTER (HIOKI)] from
50 Hz to 5 MHz. The films were cut to circles with a radius of
1 cm and then inserted in-between two stainless steel (SS)
electrodes by spring pressure. The imaginary and real parts
(Z00 and Z') of the complex impedance (Z*) data were measured
by connecting the cell with a computer program.
2.3. Transference number measurement (TNM) and
linear sweep voltammetry (LSV)
TNM of ions (tion) and TNM of electrons (te) were measured.
The arrangement of the cell was SS| electrolyte| SS and con-
nected to V&A Instrument DP3003 digital DC power supply
and UNI-T UT803 multimeter. The applied voltage was 0.2V at
room temperature where the cell polarized with time. In the
cell, the relatively high conductive polymer electrolyte was
placed between a pair of stainless-steel blocking electrodes
(SS) to perform the measurements including both the ion (tion)
and the electron (te) transference numbers through the
following relationship:
Ii  Iss
tion ¼
Ii
te ¼ 1  tion
935
where Iss and Ii are the steady-state current and initial current,
respectively.
The electrochemical stability window (ESW) was measured
using a LSV employing a DY2300 potentiostat at a scan rate of
10 mV s1 and potential in the range of 0e2.5 V.
2.4. EDLC fabrication
A planetary ball miller was used to grind and mix 3.25 g of
activated carbon (AC) and 0.25 g of carbon black (CB) for
20 min. Meantime, 0.5 g PVdF was dispersed in 15 mL NMP for
few hours. To this solution, the carbon powder was added and
then stirred for 2 h until a thick black solution was obtained.
The resulting solution was maintained with a pre-cleaned
aluminum foil. The doctor blade was used during the
coating process. Subsequently, in an oven at 60
C, the elec-
trode was dried and later stored in a desiccator.
EDLC characterization
The activated carbon (AC) electrodes were cut to circles with
an area of 2.01 cm2. The uppermost conducting sample was
inserted between the electrodes and then placed in a CR2032
coin cell. After that, the cell was put in a Teflon case as
depicted in Fig. 1.
Digi-IVY DY2300 potentiostat was performed to conduct
cyclic voltammetry (CV) of the EDLC device. The applied po-
tential varied in the range of 0e0.9 V at various scan rates. The
rechargeability of EDLC was examined at a current density of
0.5 mA/cm2 by NEWARE battery cycler for 300 cycles.
3. Results and discussion
3.1. Impedance and ion transport study
The DC conductivity of polymer electrolytes was tested via
electrochemical impedance spectroscopy. Ion-conducting
electrolytes as specific categories of materials have attracted
the attention of many research groups due to their utilization
in electrochemical energy devices over the last decades
[36e38]. Electrochemical impedance spectroscopy (EIS) is
normally used to see responses (semicircle and spike) of the
samples at high and low-frequency regions, respectively.
These ranges of response are associated with the conduction
of ions in the bulk of the electrolyte and the impact of elec-
trode polarization, respectively [39]. In the current study, in-
sights into ion migration can be provided from the electrical
Top Coin Cell
Electrolyte Film Teflon Case
Stainless Steel Bottom Coin Cell
(1)
AC Electrode
(2) Fig. 1 e Schematic diagram of EDLC setup.
936 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6

equivalent circuit (EEC) model. The modeling of the whole where C is the capacitance of CPE, u is the angular frequency
conduction system is simple and it is under intensive study and p is generally the measure of deviation of the plot from the
[40e43]. Fig. 2(a-c) presents the EEC models corresponding to axis.
impedance plots of all films. This modeling of the conduction The imaginary and real (Zi and Zr) of the impedance related
system that obtained experimentally from EIS data can be to the EEC (inset of Fig. (3a)) are interpreted as:
fitted in an attempt to gain the EEC model. Lowering the Rb  
value with the addition of plasticizer is associated with the Rb 2 C1 up1 cos pp2 1 þ Rb
dissociation enhancement of KI salt and also disruption of Zr ¼   (4)
2Rb C1 up1 cos pp2 1 þ Rb 2 C1 2 u2p1 þ 1
hydrogen bonds within the polymer chains. This enhance-
ment in conductivity from creating the amorphous phase  
within polymer electrolyte facilitates ion conduction, and R2b C1 up1 sin pp21
thus increases the number of free ions. The impedance of CPE Zi ¼   (5)
2Rb C1 up cos pp2 1 þ R2b C21 u2P1 þ 1
(ZCPE) is based on the following relationship [44,45]:

1 h pp ppi The Zr and Zi associated with the EEC as presented in the
ZCPE ¼ cos  i sin (3) inset for PVKI1 and PVKI2 of Fig. 2 are interpreted as:
Cup 2 2

Fig. 2 e Simulated EIS plots for all PVKI electrolytes.

 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6 937

PVKI4 and PVKI5) the semi-circle is usually disappearing and

only a spike exists. Generally, in impedance plot the semi-
circle can be considered as a parallel combination of Rb and
CPE, and the spike is equivalent to a capacitive element with
its intersection on the real axis as a Rb in series. Consequently,
upon the addition of 30, 40, and 50 wt.% of glycerol, the con-
ductivity was improved, which resulted in appearing only a
spike in the impedance plot for those samples.
The calculated Rb and CPE values for the PVKI1, PVKI2,
PVKI3, PVKI4, and PVKI5 electrolytes are presented in Table 2.
The high values of CPE2 with the addition of glycerol can be
explained on the basis of increasing the number of ions in the
electrolytes. This results in an increase in the accelerating
electrode polarization; thereby, an increase in the capacitance
value at low frequency [46]. The addition of glycerol as a
plasticizer enhances salt dissociation and hence increases ion
mobility [47,48].
From Eq. (6), the ionic conductivity (s) can be calculated as
Fig. 3 e Simplified circuit diagram for the TNM the measure of the electrical properties of the electrolytes.
measurement. The calculation also comprises Rb, t, and A values as charge
resistance, thickness, and surface area, respectively. From
Table 2, the conductivity values for the electrolytes are
    expressed by:
Rb 2 C1 up1 cos pp21 þ Rb cos pp2 2
Zr ¼   þ (6) t
C2 up2 s¼ (10)
2Rb C1 up1 cos pp21 þ Rb 2 C1 2 u2p1 þ 1 A  Rb
Marf et al. [49] have shown the dependency of the ionic
   
R2b C1 up1 sin pp2 1 sin pp2 2 conductivity of the electrolytes on the flexibility of the poly-
Zi ¼   þ (7) mer chain and the extent of ion mobility. Moreover, the
2Rb C1 up1 cos pp2 1 þ R2b C21 u2P1 þ 1 C2 up2
addition of glycerol as a plasticizer into this polymer electro-
lytic system facilitates all contributors in the value of con-
Here C1 is the bulk capacitance of CPE1, C2 is the capaci-
ductivity. The highest conductivity value was recorded for the
tance of CPE2 at the interface between electrodeeelectrolyte.
PVKI4 electrolyte. As its clear that the Glycerol plasticizer has
p1 shows the deviation of semi-circle diameter from the x-
been shown to improve DC conductivity by two orders of
axis; while, p2 shows the deviation of the spike from the y-
magnitude in this study. Glycerol has multi hydroxyl (OH)
axis, in other words it presents the inclination of the spike
moiety structure which acts as an alternative pathway for free
from the imaginary axis. The EEC fitting parameters are
ion from the salt to move in the polymer electrolytes. Thus,
indicated in Table 1.
Glycerol has many OH groups to dissociate more salt and
The EIS response of electrolytes possesses the only spike
destroying the inter and intra-hydrogen bonding that exists in
and the Rb is in series with CPE. The mathematical basis of the
the polymer matrix and consequently increasing the amor-
impedance can be expressed as follows:
phous phases, which are essential for the ion transport pro-
  cess. Based on the conductivity value, PVKI4 electrolyte is
cos pp
2
Zr ¼ þ Rb (8) eligible for the ion-conducting device applications, requiring
Cup conductivity series in 103 to 105 S/cm range [50].
  From impedance data containing a spike only, the trans-
pp
sin 2 port parameters of diffusion coefficient (D), mobility (m), and
Zi ¼ (9)
Cup number density (n) of ions can be determined using a number
of equations [51]. First, to calculate D of ionic species, the
The equations are also used in the fitting parameters (CPE)
following relationship is used
and measured the Rb values precisely. In the case of high
conducting electrolyte systems (in our case samples PVKI3,

Table 2 e Room temperature ionic conductivity and

circuit elements for the plasticized polymer electrolytes
Table 1 e Circuit elements for EEC simulation. (PPEs).
Sample p1 p2 k1 k2 Sample s (S/cm) Rb (U) CPE1 (F) CPE2 (F)
6 9
PVKI1 1.25 0.95 4.00  10 8
3.70  105
PVKI1 2.42  10 6380 2.50  10 2.70  106
PVKI2 1.35 1.05 3.50  108 9.20  104 PVKI2 1.41  104 109 2.86  109 1.09  105
PVKI3 e 1.18 e 1.18  105 PVKI3 5.71  104 27 e 8.47  106
PVKI4 e 1.03 e 2.76  104 PVKI4 6.71  104 23 e 3.62  105
PVKI5 e 1.09 e 5.25  104 PVKI5 4.67  104 33 e 1.90  105
938 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6

n o
2
D ¼ D
exp  0:0297½ln D
  1:4348 ln D
 14:504 (11)

!
4k2 l2
D
¼ (12)
Rb 4 umin 3

where l is the electrolyte thickness, umin is the angular fre-

quency at the minimum Zi value.
The mobility (m) of the ionic species is determined from Eq.
(13),
 
eD
m ¼ (13)
Kb T

Where T is the absolute temperature and kb is the Boltzmann

constant.
Since DC conductivity of ions is obtainable from this
equation shown below,

sDc ¼ nem (14)

The density of ion carriers (n) can be determined from Eq.

(14).
Table 3 presents all parameters related to the ion transport
and umin values for all the electrolytic systems. It is seen that
the value of D increases as glycerol quantity is increased from
10 to 40 wt.% and also the same trend is seen for m. These
increases of D and m can be ascribed to the chain flexibility
enhancement in the existence of glycerol. When the glycerol
quantity is increased, the values of D, m, and n increase which
in turn results in an increase in conductivity. To explain this,
glycerol molecules enhance the dissociation of salts, thus
increasing the number density of ion carriers [51] and glycerol
molecules lower the attraction force between the anions and
cations of the salt [52]. As a consequence, a higher number of
potassium ions (ni) is generated by KI into the polymer. Fig. 4 e Current polarization as a function of time for (a)
It was recorded that [52] the dielectric constant of polymer PVKI4 and (b) PVKI5.
electrolytes increases as going to a lower frequency value and
thus the capacitance value increases. Consequently, the
capacitance is also increased with the addition of glycerol.
electrolyte is shown. The high value of the initial current is
3.2. Electrolyte characterization for ions and breakdown related to the contribution of both charge carriers; electron
voltage and ion at the initial stage. It is also noted that there is a
substantial decrease in the current prior to a steady-state. It is
3.2.1. Transference number measurement (TNM) worth-mentioning that ionic blocking induced by stainless
The TNM is used to evaluate the identity of the main charge steel electrodes permits the electrons to go through [53].
carrier species within the polymer electrolyte. Fig. 3 depicts Eqs. (1) and (2) are used to determine the values of tion and
the circuit configuration for the TNM measurement. From the te. It is of great importance to have a tion value that closes to
current plot against time (see Fig. 4 (a, b)) it can be noted that unity which is an ideal case. From Fig. 4a it is clear that PVKI4
the current decreases until a steady-state were reached by film has higher ion carriers (tion ¼ 0.969), and the tion value for
applying the 0.2 V. From this figure, the graph of polarization the PVKI5 film has found to be (tion ¼ 0.944). As a result, it can
current against time for the relatively large conducting be concluded that the process of ion migration is the major
charge carriers in the PVA:KI:Glycerol system.
These findings are comparable to the system of Potato
Table 3 e The values of D, m, and n at room temperature. starch (PS)-methylcellulose (MC) blend SPEs incorporated with
Sample D (cm2 s1) m (cm2 V1 s) n (cm3) ammonium nitrate (NH4NO3) and glycerol in the form of
PVKI1 1.44  107 5.63  106 2.68  1018 plasticizer (PS-MCeNH4NO3eglycerol-based electrolytes) [54].
PVKI2 3.49  107 1.36  105 6.50  1019 The present study shows the ionic transference number is
PVKI3 6.14  107 2.39  105 1.49  1020 close to the previous reports. Polu et al. [55,56] used PVA-
PVKI4 6.74  107 2.63  105 1.59  1020 Mg(CH3COO)2 and PVA-Mg(NO3)2 with the ionic transference
PVKI5 5.54  107 2.16  105 1.35  1020
numbers of 0.96 and 0.98, respectively were obtained. Wang
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6 939

et al. [57] studied PVA-LiTFSI-EMITFSI with an ionic trans-

ference number of 0.995. In the present work, the value is
greater than that achieved by Ghosh et al. [58], in which the
transference number of (PEO-be(PMMA-ranePMAALi)) was
0.89 at room temperature. In another study, the transference
number in PEO/LLZTO/LiBOB polymer electrolyte was found to
be 0.57 that carried out by Guo et al. [59].
From the obtained tion, and the values of s, m and D pre-
sented in Table 3 the mobility and diffusion coefficient of
anions and cations of PVKI4 and PVKI5 systems were deter-
mined using Eqs. (15e20) [60,61].
Fig. 5 e TNM and LSV Cell configuration.
D ¼ Dþ þ D (15)

 threshold voltage, the current flow through the cells. Shukur

Dþ et al. [64] recorded 2.1 V as a decomposition voltage of lithium
tion ¼ Dþ ðDþ þ D Þ0ðDþ þ D Þ ¼ (16)
tion
salt-based biopolymer electrolyte. Thus, the potential stability
From Eqs (15) and (16), of the relatively high conducting electrolyte in this work is
eligible for energy storage device utilizations.
Dþ ¼ ½tion   ½D (17)

Regarding the motilities associated with cations and
anions:

m The CV can be used to calculate the capacitance of EDLC. In
tion ¼ mþ ðmþ þ m Þ0ðmþ þ m Þ ¼ þ
tion
m ¼ mþ þ m
From Eqs (18) and (19), it is easy to get the value of mþ as
follows:
mþ ¼ ½tion   ½m
where D-, Dþ, mþ, and m- are anion diffusion coefficient, cation
diffusion coefficient, cation mobility, and anion mobility,
respectively. The cations sizes are minor than the dimension
of anions, and consequently mþ is elevated than the m. Table 4
indicates that the mþ and Dþ are superior to the m and D. The
similar mode is evidenced for D and Dþ. Hence, the TNM
demonstrates that the conductivity is influenced by diffusion
coefficient and mobility. The PVKI4 has the uppermost
mobility and diffusion coefficient in compare with the PVKI4
system.
3.3. EDLC characteristics
3.3.1. Cyclic voltammetry (CV)
(18)
current study a scan rate of 50 mV/s in the potential window
between 0 and 0.9 V, was used for the fabricated EDLC as
(19) shown in Fig. 7. It is also noticed that there is no feature of
redox peak, suggesting cations and anions of KI salt absorp-
tion at the surface of the carbonic electrodes other than the
intercalation/deintercalation process [65e67]. This means
(20) that the non-Faradaic process takes place where ions at the
interfacial region accumulate [68]. The electric double layer
formation in the fabricated EDLC device is schematically
presented in Fig. 8. Another important feature of the CV
response is a leaf-like shape that is not perfectly rectangular.
However, it is convincing by taking into consideration of
electrode roughness and internal resistance [69,70]. This is the
desired mechanism of charge storing in EDLCs. In other
words, ion accumulation at the interface region by absorption
at the electrode surface is preferred [71e73]. One more
observation, EDLCs are superior over Faradaic capacitor or

3.2.2. Linear sweep voltammetry (LSV) measurement

The LSV is a straightforward technique that is used to deter-
mine the potential window of the polymer electrolyte prior to
utilization in energy storage device applications, with the cell
arrangement presented in Fig. 5. The LSV response of the
relatively high conducting (PVKI4) electrolyte is illustrated in
Fig. 6. It can be seen that no current is observed below 1.58 V,
indicating no electrochemical reaction occurrence within this
potential window. The polymer electrolyte decomposition
occurs beyond 1.58 V [62]. Monisha et al. [63] said that at the

Table 4 e Diffusion and motilities associated with cation

and anions.
Sample Dþ D- mþ m-
(cm2 s1) (cm2 s1) (cm2 V1 s) (cm2 V1 s)
Fig. 6 e Determination of breakdown voltage though the
PVKI4 6.53  107 2.09  108 2.54  105 8.15  107 LSV pattern of the highest conducting polymer electrolyte
PVKI5 5.23  107 3.10  108 2.04  105 1.21  106
(PVKI4).
940 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6

Table 5 e Variation in capacitance value with respect to

scan rate for the fabricated EDLC device.
Scan rate (mV/s) Capacitance (F/g)
100 23.319
50 38.272
20 59.899
10 72.245

shape of CV is quite comparable to other biopolymer-based

EDLC studies previously [79,80].

3.3.2. Chargeedischarge study

Fig. 7 e Cyclic voltammetry behavior at different sweep
rates for the highest conducting electrolyte (PVKI4).
pseudo-capacitor on the basis of relatively higher power
density, stability, thermal stability, higher reversibility, cost-
effective, safer, and more facile fabrication methods [74e76].
On the other hand, it is proved that the role charge transfer
(Faradaic process) is absent from the nonexistence of redox
peak whereas involved in fabricated SCs [77]. This can be
correlated to the porosity of activated carbon as well as in-
ternal resistance [78]. The specific capacitance (Cspe) of the
EDLC assembly can be obtained from the CV response via the
following equation, and it was found to be scan rate depen-
dent as shown in Table 5 [65e67]:
ZVf
IðVÞdV
Cspe ¼  
2mv Vf  Vi
Vi
Where I(V)dV refers to the area of the CV response, which is
calculated by Origin 9.0 software via the integration function.
In this work, Vi and Vf are set to 0 and 0.9 V, respectively. The m
and v parameters refer to the mass of active material used and
sweep rate, respectively. Herein, the Cspe of the fabricated
EDLC is 72.245 F g1 that can be compared to the Cspe (79.136) at
300 cycle from chargeedischarge response. In this work, the
The rechargeability of the EDLC was analyzed by applying
0.2 mA/cm2 with recording 300 cycles as shown in Fig. 9. At the
beginning of applying the current, the charged ions start to
migrate from the bulk region of the electrolyte to the interface
region; forming double layer charging which is known as
capacitive characteristic [81,82]. Fig. 9 confirms the capacitive
behavior of the assembled EDLC from linear discharge curve
response. From the chargeedischarge response, the specific
capacitance (Cs) of the fabricated EDLC can be determined
using the following equation:
i
CCD ¼ (22)
sm
Where s and i, are gradient of the discharge region and current
applied, respectively. At the 1st cycle, the Cs was found to be
152.4 F/g and lowered to 79.138 F/g at the 300th cycle as pre-
sented in Fig. 11. This drop in the value of Cs can be related to
inhomogeneity of the electrolyteeelectrode region [83e85]. An
interesting observation is that beyond 100th cycle, the value of
Cs becomes constant which is so-called ion polarization sta-
(21) bilization state. Table 6 presents Cs values of a number of
fabricated EDLC devices based on various polymer
electrolytes.
It is noted that the voltage drops prior to the discharging
process commence as shown in Fig. 9. This shows the internal
resistance of the fabricated EDLC, in which the ESR was ob-
tained using the following equation.
Vd
ESR ¼ (23)
i
Cell Ptential (V)

Time (s)
Fig. 8 e Electric double layer formation in the charged EDLC
device. Fig. 9 e Chargeedischarge profile of the fabricated EDLC.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6 941

Table 6 e Relative specific capacitance values of a number

of proton-based EDLC systems.
SPE system Cs (F/g) Cycles Reference
Chitosan-H3PO4eAl2SiO5 0.22 100 [88]
Chitosan-H3PO4eNH4NO3eAl2SiO5 0.25 100 [88]
PVA-NH4C2H3O2 0.14 Not stated [89]
MC-NH4NO3 1.67 100 [90]
PEO-LiTf-EMITf 1.70 Not stated [91]
PEOe KOHeH2O 90 Not stated [92]
PVA-KOH 100 1000 [93]
PVA:KI:glycerol 152 300 This work

15th cycle, the efficiency is stabilized at an average of 96.1% up

Fig. 10 e Equivalent series resistance (ESR) of the fabricated
EDLC over 300 cycles.
where Vd is the drop potential. The value of ESR is expected to
be within the range of 64e136 U, as revealed in Fig. 10. This
value is relatively high as a consequence of the presence of
PVdF in the electrode composition. This polymer as an insu-
lator prevents electron migration in the carbonic electrons
[86,87].
The cycle stability of the EDLC can be detected from the
consistent value of efficiency. Apart from being consistent, the
efficiency of an excellent EDLC is large which reaches more
than 95%. The efficiency of the fabricated EDLC is plotted in
Fig. 12. An efficiency of 81.2% can be seen at the 1st cycle and it
increases to 97.5% at the 15th cycle. Normally, at initial cycle
numbers, the charging process is longer than discharging.
Ions started to migrate towards the surface of the electrode
and be familiar with the pathway of the conduction. This
stage usually gives unstable and low efficiency. Beyond the
to 300 cycles. The large magnitudes of efficiencies signify that
discharging time is longer or similar to charging time. This
result indicates that the EDLC in the present work has excel-
lent stability and electrolyteeelectrode contact.
Fig. 13 show that the energy density (E) at the 1st cycle is
17.3 Wh/kg. The E value achieved through this formula:
Cs V 2
E¼ (24)
2
The E is then decreasing to 13.2 Wh/kg and stabilized at an
average of 10 Wh/kg from the 200th cycle to the 300th cycle.
Hence, it can be assumed that beyond the 40th cycle the
conduction of ion has almost the same energy barrier [64]. The
E in this work is comparable to other EDLC reported using
various materials. Hina et al. [94] reported that the value of E
for their EDLC is in the range of 9.82e21.6 Wh/kg depending on
the concentration of lithium triflate (LiTf). EDLC by Mazuki
et al. [95] achieved 1.19 Wh/kg for the CMC-PVA-NH4Br sys-
tem. The high E could be due to the presence of plasticizer in
this work. The outcomes of this work reveal that synthetic
biopolymer-based electrolytes are important for energy stor-
age applications. Moreover, the power density (P) values are
calculated if ESR values are known which can be seen in
Fig. 14. The values were calculated using the following
equation:
V2
P ¼ (25)
4mðESRÞ
Efficiency %

Cycle number

Fig. 12 e Columbic efficiency plot of the fabricated EDLC

Fig. 11 e Specific capacitance trend throughout 300 cycles. over 300 cycles.
942 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 3 : 9 3 3 e9 4 6
Energy density (Wh/kg)
Cycle number
Fig. 13 e E plot of the fabricated EDLC for 300 cycles.
Power density (W/kg)
Cycle number
Fig. 14 e P plot of the fabricated EDLC for 300 cycles.
The P value at the 1st cycle is determined to be 1291.98 W/
kg and it drops to 883 W/kg as the EDLC finished 100 cycles.
The pattern of P is in good agreement with the ESR trend. This
is due to the degradation of electrolyte that happens when the
resistance raises, causing the ionic aggregation resulted from
the rapid process of charging/discharging, thus causing
decreased P at a high cycle number [96]. The values of E and P
are obviously reliant on the active material's mass loading in
the fabrication of EDLC. The quite low current and small mass
loadings are documented to be responsible for producing
improved electrochemical performance [97].
4. Conclusion
This work included the fabrication of an EDLC device using
plasticized PVA polymer electrolyte doped with KI and plas-
ticized with different concentrations of glycerol plasticizer
served as both electrolyte and separator. The PEs were pre-
pared using the solution casting technique at ambient tem-
perature. Through the impedance study, the ionic
conductivity of the samples was explored, and it was found
the (PVKI4) sample exhibited the highest DC conductivity. The
dominant ion transference number close to unity (0.969) for
the (PVKI4) was found to be very desirable to be employed in
the EDLC device. In addition, the sample (PVKI4) also exhibited
a wide potential window of 1.58 V, which is preferable for
many electrochemical devices. The leaf shape CV plot with
the absence of any redox peaks confirmed the pure non-
faradic process with the electric double layer formation at
the electrodeeelectrolyte interface. The fabricated EDLC has
shown a high specific capacitance of 152 F/g, and excellent
Columbic efficiency of 96.1% over 300 cycles. The energy and
power density of the EDLC at the first cycle were found to be
17.3 Wh/kg and 1743.4 W/kg, respectively. These values were
dropped to 10 Wh/kg and 560 W/kg were 300 cycles reached,
due to rapid charge/discharge process in which degradation of
electrolyte occurs because of the ohmic drop, which in turn
result in ionic aggregation. Overall, the prepared solid polymer
electrolytes are looking promising for employment in the
EDLC; however, further enhancement in the conductivity and
stability of the prepared polymer electrolytes are needed for
the better performance of the EDLC device in the future.
Declaration of Competing Interest
The authors declare no conflict of interest.
Acknowledgments
We would like to acknowledge all support for this work by the
University of Sulaimani, King Saud University and Komar
University of Science and Technology. The authors (S. M.
Alshehri, T. Ahmed) are grateful to the researchers supporting
project number (RSP-2020/29), King Saud University, Saudi
Arabia for funding.
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