Ionics (2023) 29:4243–4252

https://doi.org/10.1007/s11581-023-05122-8

RESEARCH

Plasticized lithium iodide‑doped polyacrylonitrile‑methylcellulose

blend electrolytes for supercapacitor application
N. A. Shamsuri1 · Z. E. Rojudi2,3 · V. T. Vicxeant4 · I. M. Noor2,3 · M. F. Z. Kadir1,5 · M. F. Shukur6,7

Received: 16 March 2023 / Revised: 21 June 2023 / Accepted: 7 July 2023 / Published online: 15 July 2023
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023

Abstract
This paper reports the characterisation and application of plasticized polyacrylonitrile (PAN)-methylcellulose (MC) doped
with lithium iodide (LiI) in a symmetric supercapacitor at ambient temperature. From Fourier transform infrared spectroscopy
(FTIR) analysis, the shifting of hydroxyl (OH) band to a lower wavenumber upon addition of glycerol to the PAN-MC-LiI
evidences the interaction between the materials at OH groups. X-ray diffraction (XRD) analysis reveals that the electrolyte
with 20 wt.% glycerol (PMG20) has the lowest degree of crystallinity. This XRD result reflects the increase in conductiv-
ity as PMG20 obtains the highest room temperature conductivity of (1.54 ± 0.40) × ­10–3 S ­cm−1. Field emission scanning
electron microscopy (FESEM) analysis shows that there are changes in surface morphology as LiI and glycerol are added
to PAN/MC. The tion of PMG20 is 0.93 indicating that the ions are the dominant charge carriers. From linear sweep voltam-
metry (LSV), PMG20 is electrochemically stable up to 2.1 V. An electrochemical double layer capacitor (EDLC), which
is a type of supercapacitor, is fabricated by sandwiching PMG20 between a pair of activated carbon-based electrodes and
is characterised using cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD) analysis. The highest specific
capacitance of single electrode (Csp) obtained from CV is 16 F g­ −1. The EDLC is charged and discharged for 100 cycles at
1.0 mA ­cm−2 with Csp between 28.08 and 15.76 F ­g−1.

Keywords Polyacrylonitrile · Methylcellulose · Lithium iodide · Glycerol · Supercapacitor

* M. F. Shukur
mfadhlullah.ashukur@utp.edu.my
1
Physics Department, Faculty of Science, Universiti Malaya,
50603 Kuala Lumpur, Malaysia
2
Physics Department, Ionic Materials and Energy Devices
Laboratory, Universiti Putra Malaysia, 43400 UPM Serdang,
Selangor, Malaysia
3 Optimising ionic conductivity of SPE is the key towards
Physics Division, Centre of Foundation Studies
for Agricultural Science, Universiti Putra Malaysia,
43400 UPM Serdang, Selangor, Malaysia
4
HP Malaysia Manufacturing Sdn. Bhd. PMT 731 Persiaran
Cassia Selatan 2 Taman Perindustrian Batu Kawan,
11400 Pulau Pinang, Malaysia
5
University Malaya Centre for Ionic Liquids (UMCiL),
Universiti Malaya, 50603 Kuala Lumpur, Malaysia
6
Centre of Innovative Nanostructure and Nanodevices
(COINN), Universiti Teknologi PETRONAS,
32610 Seri Iskandar, Perak, Malaysia
7
Department of Fundamental and Applied Sciences, Universiti
Teknologi PETRONAS, 32610 Seri Iskandar, Perak,
Malaysia
Introduction
Liquid electrolytes are used conventionally in energy storage
devices owing to their high ionic conductivity. However, due
to high volatility and flammability, the presence of solvents
in liquid electrolyte leaves risk of leakage and safety issues
[1, 2]. These shortcomings can be overcome by using dry
electrolyte system known as solid polymer electrolyte (SPE).
high performance energy storage devices [3]. Methods such
as polymer blending and plasticization have been introduced
to enhance the ionic conductivity of the SPE [4, 5]. Polymer
blending is done by combining two or more polymers, in
which secondary bonds can take place. Polymer blending
can improve the thermal and electrical properties of polymer
films [6]. Incorporation of low molecular weight and high
dielectric constant plasticiser such as glycerol into the poly-
mer films can increase the number of charge carriers leading
to ionic conductivity increment [7].
Polyacrylonitrile (PAN) is a semicrystalline polymer from
the resin family prepared by the polymerisation of acrylonitrile.

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4244 Ionics (2023) 29:4243–4252

The nitrile groups, with lone pair electrons at the nitrogen atom, added to the highest conducting plasticiser-free electrolyte
act as hydrogen bonding acceptor [8]. PAN-based films are solutions and stirred for 1 h at room temperature until the solu-
reported to exhibit high ionic conductivity, excellent physical tions become homogeneous. The homogenous solutions were
properties and good morphology [9]. Methylcellulose (MC) is transferred onto glass Petri dishes and dried in an oven at 80 °C
a methyl ester of cellulose [10]. MC is recognised for its cost- for 20 h. The formed films were kept in desiccators filled with
effectiveness, eco-friendliness and desirable film-forming char- silica gel desiccants before characterised. The designation and
acteristics. MC contains functional groups of C–O–C, O–H and composition of the electrolytes were listed in Table 1.
O-CH3. These functional groups are able to form dative bond
with cations of dopant which are responsible for ionic conduc- Electrolyte characterisation
tion [11]. In previous work [12], unplasticized PAN-MC blend
electrolytes doped with lithium iodide (LiI) obtained maximum The Fourier transform infrared spectroscopy (FTIR) spec-
conductivity of (8.12 ± 1.57) × ­10–4 ­Scm−1. tra of electrolytes were carried out using Perkin Elmer,
Lithium iodide (LiI) is a common doping salt in polymer Spectrum One spectrometer in a wavenumber range of 550
electrolytes for various energy applications. When incorporated to 4000 ­cm−1 at a resolution of 4 ­cm−1. X-ray diffraction
into a polymer matrix, LiI can enhance the ionic conductiv- (XRD) analysis was carried out using PANalytical X’Pert3
ity and electrochemical performance of SPE-based devices. As Powder with Cu Kα radiation of 1.5406 Å wavelength. The
reported in [13], the optimum conductivity of corn starch doped 2θ angle was varied from 5° to 80°. From the diffraction
with LiI was 1.82 × ­10–4 S ­cm−1, higher than that of starch with data, the crystallite size (L) and the degree of crystallinity
lithium acetate (2.07 × ­10–5 S ­cm−1) [14]. LiI exhibits a lattice (Xc) were calculated using the following equations:
energy of 757 kJ ­mol−1, which is lower than that of lithium
0.9𝜆
acetate (881 kJ ­mol−1), lithium chloride (865 kJ ­mol−1), and L= (1)
𝛽cos𝜃
lithium bromide (807 kJ ­mol−1) [15]. The low lattice energy of
lithium iodide implies that less energy is required to break the
ionic bond between the anion and cation. In this case, more ions Ac
Xc (%) = × 100% (2)
can be dissociated which can contribute towards conductivity AT
enhancement [16]. In this work, glycerol plasticiser was incor-
where λ is the wavelength of X-rays, β is the full width at
porated into PAN-MC-LiI. Glycerol is a non-toxic compound
half maximum (FWHM) of the XRD peaks, θ is the diffrac-
with high boiling point (290 °C) and low melting point (18 °C),
tion angle, Ac is the area of the crystalline region, and AT is
which can prevent glycerol molecules from vaporisation and
solidification in the SPE at room temperature [17]. High die- the total area of the XRD patterns. The Ac was determined
lectric constant (42.5) can weaken the attraction between the using Nara-Komiya (N-K) method. The electrochemical
cations and anions thus assisting the dissociation of salt [18]. impedance spectroscopy (EIS) measurements were analysed
Two main types of supercapacitors are pseudocapacitor using Metrohm Autolab in a frequency range of 50 Hz to
and electrochemical double layer capacitor (EDLC) [19]. In 1 MHz at room temperature. The Nyquist plots obtained
pseudocapacitor, energy is stored electrochemically via redox were used to determine the bulk resistance (Rb). The conduc-
reactions whilst in EDLC, energy is stored electrostatically via tivity of the electrolytes was determined using the equation:
formation of Helmholtz double layer. EDLC usually incorpo- t
rates materials such as activated carbon, and carbon nanotubes
𝜎=
Rb A (3)
(CNTs) and graphene as electrode. EDLC has high power
density, high durability, excellent thermal stability and longer
charge time [20]. In this work, the electrolytes were character-
ised using EIS, FTIR and XRD in order to identify the most
conductive electrolyte. The highest conductive electrolyte was Table 1  Composition of plasticized PAN-MC-doped LI polymer
used in the application of EDLC. electrolyte
Designation PAN (g) MC (g) LiI (g) Glycerol Glycerol (g)
(wt. %)
Experimental
PMG0 0.25 0.25 0.5 0 0
PMG10 0.25 0.25 0.5 10 0.111
Electrolyte preparation
PMG20 0.25 0.25 0.5 20 0.250
PMG30 0.25 0.25 0.5 30 0.429
The preparation of plasticiser-free LiI-doped PAN-MC blend
PMG40 0.25 0.25 0.5 40 0.667
electrolytes was reported in the previous work [12]. In this
PMG50 0.25 0.25 0.5 50 1.000
work, desired amounts of glycerol (R&M Chemicals) were

13
Ionics (2023) 29:4243–4252
where t is the thickness of the electrolytes, Rb is the bulk
resistance, and A is the electrode–electrolyte contact area.
The surface morphology of the electrolytes was examined
at × 1 K magnification using a Zeiss Supra 55Vp field emis-
sion scanning electron microscope. Transference number
measurement (TNM) was conducted using the polarisation
method to evaluate the transference number of ion (tion) and
the transference number of electron (te). In TNM, the most
conducting electrolyte was placed between two stainless stell
electrodes under spring pressure. The time-dependent direct
current (dc) was monitored using a UNI-T UT803 digital
multimeter at a potential of 0.20 V at room temperature. A
Digi-IVY DY2300 potentiostat was employed to perform
linear sweep voltammetry (LSV) at a scan rate of 5 mV ­s−1.
LSV was done using a two-electrode configuration system
with stainless steel electrodes at a voltage range of 0 to
3.0 V.
Preparation of electrode
Two grams of polyvinylidene fluoride (PVDF) (Aldrich),
1 g of carbon black (Alfa Aesar) and 13 g of activated car-
bon (RP20) were mixed in 60 ml of N-methylpyrrolidone
(NMP) at 50 °C under continuous stirring for 30 min.
Aluminium foil as current collector was coated with the
electrode slurry at a thickness of 0.25 mm. The electrode
was then dried at 70 °C for 1 h. The dried electrode was
kept in a desiccator filled with silica gel before use.
EDLC fabrication and characterisation
The EDLC was fabricated by sandwiching the highest con-
ducting electrolyte with a pair of activated carbon electrodes.
The surface area of an electrode was 2.25 c­ m2 and the total
mass of electrodes is 0.018 g. The Perspex plates were
used to hold the EDLC cell. The EDLC performance was
analysed using cyclic voltammetry (CV) and galvanostatic
charge–discharge (GCD) employing Metrohm Autolab.
Results and discussions
Fourier transform infrared spectroscopy (FTIR)
The FTIR analysis were done to identify the type of inter-
action between PAN-MC-LiI and glycerol. Figure 1 illus-
trates the FTIR spectra of plasticized PAN-MC-LiI elec-
trolytes. From our previous work [12], addition of LiI salt
shifted the hydroxyl (OH) peak of PAN-MC to a lower
wavenumber of 3411 ­cm−1. The interaction between the
cation of salt and oxygen atom of OH through dative bond
4245
resulted in the changing of frequency of OH vibration.
This phenomenon led to the shifting of OH peak. Addition
of glycerol plasticiser was expected to increase the num-
ber density of ions thus more ions can interact with OH
molecules. This hypothesis is evidenced by the shifting
of OH peak. On addition of 10 wt.% glycerol (PMG10),
the OH peak has shifted to 3389 ­cm−1. As the concentra-
tion of glycerol increases up to 50 wt.%, the OH peak has
shifted to a lower wavenumber of 3330 ­cm−1. The peak
of C≡N (nitrile) stretching band in the FTIR spectrum
of PMG0 appears at 2245 ­cm−1 which is comparable to
that reported by Nithya et al. [21], for PAN-ammonium
nitrate ­(NH4NO3). No shifting of nitrile peak is observed
as shown in Fig. 2. However, the intensity of nitrile peak
in the spectra of plasticized electrolytes is higher than that
of PMG0 (3.12%). As reported Jyothi et al., the change
in intensity of IR peak is also evidence of interaction
between the materials. The shifting of C =  = O peak is
also observed on addition of glycerol up to 50 wt.%. [22].
X‑ray diffraction (XRD)
XRD examination was done on the electrolytes to study the
effects of glycerol concentrations on the crystallinity of the
polymer electrolyte. As reported by Chai and Isa [23], that
the addition of plasticiser can reduce the degree of crystal-
linity of the polymer. Figure 3 depicts the XRD patterns for
the plasticized polymer electrolytes with different glycerol
concentrations. From XRD diffractogram of PMG10 shows
a major crystalline peak at 2θ = 22.77°, respectively. Upon
addition up to 20 wt.% glycerol, has reduced the intensity
of the peak, indicating that PMG20 is more amorphous that
Hydroxyl Group Nitrile Group
PMG50
PMG40
Transmittance (%)
PMG30
PMG20
PMG10
PMG0
4000 3310 2620 1930 1240 550
Wavenumber (cm-1)
Fig. 1  FTIR spectra for PAN-MC-LiI-glycerol complexes
13
4246 Ionics (2023) 29:4243–4252

PMG50

PMG50

3.34%
PMG40

PMG40

3.38%

Intensity (a.u)
PMG30
Transmittance (%)

PMG30

4.05% PMG20

PMG20
PMG10
4.49%

5 20 35 50 65 80
PMG10 2θ ( )

4.87% Fig. 3  X-ray diffractograms of PAN-MC-Lil-glycerol electrolytes

reported by previous work [12], the crystallite size of PMG0

is 1.98 nm. With the addition of 10 wt.% glycerol, the crystal-
2400 2200 2000 lite size decrease to 1.18 nm. PMG20 has the smallest crystal-
lite size (0.84 nm) shows that PMG20 is the most amorphous
Wavenumber (cm-1) electrolytes. Then, the crystallite sizes increase gradually
from PMG30 to PMG50 indicating that the electrolytes are
Fig. 2  FTIR spectra for PAN-MC-LiI-glycerol complexes in the becoming more crystallite. In N-K method, an area above the
region of C≡N band baseline curve is represented the crystalline region whilst area
under the baseline curve is represented the amorphous region
PMG10. These results show that the existence of glycerol in between 5° and 80° as illustrated in Fig. 4.
the polymer electrolyte assists in the dissociation of the salt
ions and reduces salts recrystallization [24]. The increase in Electrical impedance spectroscopy (EIS)
amorphous phase in the polymer results in higher conductivity
because the amorphous structure offers larger ionic diffusiv- EIS is a non-destructive and reliable method to study
ity [25]. Further addition of glycerol has shown an increase the electrical properties of polymer electrolyte. In
in the intensity of the peak and development of new peaks at this work, EIS was used to study the conductivity of
2θ =  ~ 16°. The XRD pattern of PMG30 shows and increase
in the intensity where it can be seen to increase gradually
up until 50 wt.% glycerol. The increase in intensity of the Table 2  The crystallite size and degree of crystallinity of PAN-MC-
peaks and development of new peaks indicates that the poly- LiI-glycerol
mer electrolyte has become less amorphous. As reported by Samples Crystallite size, L (nm) Degree of
Kadir et al. [26], that the addition of glycerol above the opti- crystallinity, Xc (%)
mal wt.% has reduces the amorphousness of the electrolyte
PMG0 1.980 17.400
contributing to lower conductivity. This occurrence is due to
PMG10 1.188 15.533
the intermolecular interaction between plasticisers forming
PMG20 0.842 11.180
linkages between them causing the salt to recrystallise [27].
PMG30 0.932 13.853
To verify the crystallinity of the polymer electrolytes, crystal-
PMG40 1.822 18.738
lite size and degree crystallinity were calculated using Eqs. 1
PMG50 1.901 22.968
and 2. The results of L and Xc are tabulated in Table 2. As

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Ionics (2023) 29:4243–4252 4247

PAN-MC-LiI- glycerol at room temperature. The ionic 8.00E+02

conductivity was calculated using Eq. 3. The selected PMG10

polymer electrolytes values of Rb were obtained from the PMG20

Nyquist plot as shown in Fig. 5. The Rb value can be deter- 6.00E+02 PMG30

mined from the interception between the horizontal axis PMG40

and the inclined spike. According to Ong et al. [28], the

inclined spike at low frequency region is represented to
4.00E+02


double layer capacitance in a cell with an ion-blocking
electrode configuration. The disappears of semicircle at
high frequency region showed that the ions are the major-
Rb
ity charge carriers which shows that the total conductivity 2.00E+02

is mainly due to conduction of ion. From Fig. 5, it can be

observed that PMG20 has the lowest Rb value compared to
the others. The reduction in Rb values is due to the increase
of mobile ions in the polymer electrolyte after the addition
of plasticiser [29]. The conductivity on glycerol concen-
tration at room temperature is illustrated in Fig. 6 and
tabulated in Table 3. As reported in previous work [12],
the conductivity of PMG0 is (8.12 ± 1.57) × ­10–4 S ­cm−1.
With the addition of 10 wt.% glycerol, the conductivity
is increase to (1.06 ± 0.10) × ­10–3 S c­ m−1 and achieves a
PMG50
PMG40
PMG30
Intensity (a.u.)
0.00E+00
0.00E+00 2.00E+02 4.00E+02 6.00E+02 8.00E+02
Z 
Fig. 5  Nyquist plot of selected electrolytes
maximum value at (1.54 ± 0.40) × ­1 0 –3 S ­c m −1 with the
addition of 20 wt.% glycerol. Glycerol has multihydroxyl
structure that produces alternative pathways for ion migra-
tion thus increase the conductivity values [17]. Besides,
the addition of glycerol also promotes the increases of
charge carriers that influence the conductivity [30]. Up
to 30 wt.% glycerol, the conductivity continue decreases.
The addition of glycerol above the optimal concentration
leads to the recrystallization of salts due to formation of
microcrystalline junctions between plasticisers resulting in
reduced conductivity [29, 31]. The conductivity results are
in alignment with the XRD results. It shown that PMG20
had the smallest crystallite size and the had the highest
amorphous regions which also resulted in the highest ionic
conductivity. Polymer electrolytes with conductivity series
between ­10–5 and ­10–3 S ­cm−1 are promising application

for electrochemical devices [32]. Therefore, it can be

PMG20
1.00E-02
σ (S cm-1)

PMG10 1.00E-03

1.00E-04
5 20 35 50 65 80 0 10 20 30 40 50 60
2θ ( ) Glycerol content (wt.%)

Fig. 4  Nara-Komiya of PAN-MC-Lil-glycerol electrolytes Fig. 6  Effect of glycerol content on conductivity at room temperature

13
4248 Ionics (2023) 29:4243–4252

Table 3  Room temperature conductivity of PAN-MC-LiI at different in Fig. 7(c), the prevalence of a dark region becomes
concentrations of glycerol prominent, accompanied by the presence of linkage like
Designation Conductivity ­(Scm−1) structures indicating a high amorphous region within
the PMG20 electrolyte. This is because the plasticiser
PMG0 (8.12 ± 1.57) × ­10–4
acts as a mediator between the polymer molecules by
PMG10 (1.06 ± 0.10) × ­10–3
establishing connections with them [27]. Furthermore,
PMG20 (1.54 ± 0.40) × ­10–3
the plasticiser facilitated the ion conduction by creating
PMG30 (1.08 ± 0.23) × ­10–3
alternative pathways which contributes towards conduc-
PMG40 (6.43 ± 0.99) × ­10–4
tivity enhancement.
PMG50 (2.92 ± 0.48) × ­10–4

Transference number measurement (TNM)

concluded that the highest conducting electrolyte in this
work is suitable to be used for supercapacitor application.
Field emission scanning morphology (FESEM)
Figure 7 represents the surface micrograph images of
PAN-MC polymer blend, PMG0 and PMG20 electro-
lytes. It is evident that the PAN-MC polymer blend
exhibits a significant presence of spherulitic structures.
The presence of spherulites indicates the presence of
crystalline regions in PAN-MC polymer blend [33].
The FESEM micrograph depicted in Fig. 7(b) reveals a
smooth and uniform surface for PAN-MC incorporated
with 50 wt.% LiI. The surface becomes darker suggest-
ing the increase in amorphousness as salt was added to
the electrolyte [34]. In the FESEM micrograph displayed
In polymer electrolyte systems, electrons and ions are the
two main charge carriers. In order to determine the primary
charge carrier, TNM analysis was performed and the result
is depicted in Fig. 8. It can be seen that there is a sudden
drop in current from 14.3 to 1.0 µA. Initially, the current
was carried by ions and electrons. However, ion flow was
blocked whilst electrons were allowed to pass through by
the stainless-steel electrodes [35]. From this point, only
electrons carried the current which results in saturated or
steady-state current at 1.0 µA. The tion of the PMG20 was
determined using following equation:
Iinitial − If inal
tion = (4)
Iinitial
where Iinitial is the initial polarisation current whilst Ifinal is
the steady-state current. The tion and te of PMG20 are found

Fig. 7  FESEM morphology of

(a) PAN-MC blend, (b) PMG0 a b
and (c) PMG20 at magnification
of 1 K ×

13
Ionics (2023) 29:4243–4252 4249

16

14
14.3 µA

12

Current density (mA cm-2)

10
Current (µA)

2
1.0 µA

0
-1000 1000 3000 5000 7000 9000
Time (s)

Fig. 8  Transference number of PMG20 electrolyte at 0.2 V potential
to be 0.93 and 0.07 respectively. Thes results show that the
dominant charge carriers in the PMG20 are ions. The high
tion obtained suggests that the present electrolyte is suitable
for EDLC application.
Linear scanning voltammetry (LSV)
To be utilised in an energy device, electrochemical stability
of the electrolyte material is crucial. By operating the device
Potential (V)
Fig. 9  Linear sweep voltammetry of PMG20 electrolyte at scan rate
of 5 mVs.−1
process takes place where the ions at the interfacial region
accumulate [39]. The CV plot leads to leaf shape due to
some internal resistance of EDLC and possesses the char-
acteristics of ideal rectangular shape capacitors [40]. The
specific capacitance of single electrode (Csp) at different
scan rates was calculated using equation [29]:
Vf

Vf − Vi mv ∫
4
below the maximum operational voltage, the breakdown of Csp = ( ) I(V)dV (5)
the polymer electrolyte can be prevented, enabling extended Vi

where ∫ I(V)dV is area of the CV plot, (Vf – Vi) is the volt-

charge and discharge cycles [36]. Figure 9 depicts the LSV
curve of PMG20 from 0 to 3 V at room temperature. No sig-
age range, v is the scan rate and m is the total mass of active
nificant changes in current can be observed as the potential
material in both electrodes. The Csp values at different scan
is linearly swept from 0 to 1.5 V. This constant current is
rates is tabulated in Table 4. The highest Csp value of 16.88
attributed to the capacitive current resulting from the for-
mation of an electrochemical double layer on the surface
of the stainless steel electrodes [37]. Beyond 1.5 V, a slight 15

increase in current is observed indicating the initiation of 10 mV/s

the redox reaction. When the voltage reaches 2.1 V, a sharp 10

20 mV/s

increment in current occurs, which is ascribed to the faradaic

30 mV/s
50 mV/s
current response resulting from the redox reaction within 100 mV/s

the PAN-MC-LiI-glycerol electrolyte. The present result is 5

Current density (mA cm-2)

comparable to the report in [38] for plasticized PVA-MC-

NH4I which was used in an EDLC. The present LSV results 0

show that PMG20 is suitable to be used as a separator for

EDLC application. -5

Cyclic voltammetry (CV)

-10

The performance of EDLC using PMG20 is analysed using

CV analysis at scan rate was studied by conducting CV at -15
0 0.2 0.4 0.6 0.8 1 1.2
­ Vs−1 between
different scan rates 10, 20, 30, 50 and 100 m Potential window (V)
potential range of 0 V to 1 V as illustrated in Fig. 10. No
redox peak can be observed showed that the non-Faradic
Fig. 10  Cyclic voltammogram of EDLC at different scan rates

13
4250 Ionics (2023) 29:4243–4252

Table 4  Specific capacitance of Scan rates (mV Csp ­(Fg−1) but the shape can be diverging due to carbon roughness, electro-
EDLC at various scan rates ­s−1) lyte and internal resistance. From Fig. 8, it can be observed that
before discharging process, there is a voltage drop due to internal
10 16.88
resistance between the current collector and the electrolyte [40].
20 14.03
The Csp was calculated using the following equations [29]:
30 10.82
50 8.75 4C
Csp = (6)
100 5.79 m

⎛ ∫ tf V(t)dt ⎞
C = 2I ⎜ i V ⎟
t
1.2 (7)
⎜ V 2� f ⎟
⎝ Vi
⎠
1

where I is the constant current, V is the potential window, Vi

is the initial potential, Vf is the final potential and ∫ tf V(t)dt
Voltage (V)

0.8 t
i
0.6
is the area under the discharge curve. The Csp value for first
0.4
cycle obtained is 28.08 ­Fg−1 and drop until 15.76 ­Fg−1 for
100 cycles. It can be observed that the C sp values are
0.2 decreased as the number of charge discharge cycles increases
due to the imperfection of the electrode–electrolyte contact
0
0 100 200 300 400 500 600 [29]. The performance of other reported works using acti-
Time (s)
vated carbon materials electrode is recorded in Table 5. It
signifies that the current employed solid polymer electrolyte
Fig. 11  Charge–discharge curve for EDLC at current density of is a promising material for EDLC development.
1.0 mA ­cm−2 for ­81st to ­90th cycle

­Fg−1 was achieved at 10 m ­ Vs−1 scan rate whilst the lowest
−1
Csp value of 5.79 F
­ g was achieved at 100 m ­ Vs−1 scan rate.
As the scan rate increases, the Csp value decreases due to the
charges stored in the electrode surface decreases. Whereas,
at low scan rates, the ions have adequate time to diffuse into
vacant sites in the active electrode material which results in
higher Csp value [2]. This also develops the double layer to
form and enhances the capability of EDLC to store charge.
Galvanostatic charge–discharge (GCD)
The charging and discharging of EDLC were done at a constant
current density of 1.0 mA ­cm−2 for 100 cycles. The charge and
discharge curves appear to be approximately linear as shown in
Fig. 11 indicating that the EDLC possesses the right capacitor
energy storage system [30]. As reported by Aziz et. al [11], the
ideal charge and discharge curve of EDLC is a triangle shape
Conclusion
An EDLC system with PAN-MC blend doped with LiI salt
and plasticized using glycerol has been fabricated using
solution casting technique. From FTIR analysis, shifting
of the hydroxyl band from to a lower wavenumber proved
the interaction between the materials. XRD measurement
showed that PMG20 had the smallest crystallite size of
0.842 nm and lowest degree crystallinity of 11.18% indi-
cated PMG20 had the most amorphous region compared to
the others. PMG20 achieved the highest ionic conductivity
which was (1.54 ± 0.40) × ­10–3 S ­cm−1 at room temperature,
verified with the FTIR and XRD results. FESEM analysis
showed that on addition of glycerol, the surface morphology
of the electrolyte was transformed to linked surface and the
result was related to an increase in the amorphousness. From
TNM, the tion for PMG20 electrolyte was 0.93 indicating that

Table 5  Comparison of specific capacitance of present EDLC with other works using activated carbon materials
Electrolytes Charge–dis- Specific capacitance of single Specific capacitance of Reference
charge cycles electrode, Csp (F ­g−1) EDLC, C (F g­ −1)

Polyvinyl alcohol-MC-ammonium thiocyanate 100 14.60 - [39]

Chitosan-poly(ethylene oxide)-lithium perchlorate 100 - 6.88 [41]
Dextran-ammonium bromide 100 - 2.05 [42]
PAN-MC-LiI-glycerol 100 28.08 7.02 This work

13
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ions were the dominant conducting species. LSV measure-
ment revealed that PMG20 electrolyte decomposed at 2.1 V,
confirming the suitability of PMG20 electrolyte for EDLC
application. The electrochemical performance of EDLC
was tested through CV analysis where the specific capaci-
tance of the EDLC is 16 F g­ −1. At low scan rates, ions have
enough time to diffuse into vacant sites in the electrodes
which results in higher specific capacitance value which is
in line with the results obtained. The specific capacitance
from GCD analysis during the ­1st cycle was 28.08 F ­g−1 and
reduced to 15.76 F g­ −1 after 100 cycles indicating it has a
good cyclic stability. From the CV and GCD characteristics,
plasticized PVA/MC/LiI showed potential as candidate for
electrolyte material in EDLC, and further improvements are
underway.
Author contribution N.A. Shamsuri wrote the main manuscript text
and prepared the figures and tables and methodology; Z.E. Rojudi
wrote the draft manuscript text; V.T. Vicxeant: conceptualization
and methodology; I.M. Noor reviewed the manuscript; M.F.Z. Kadir
reviewed the manuscript and funding and M.F. Shukur: supervision,
methodology and reviewed the manuscript and funding.
Funding This study is funded by the Universiti Teknologi PETRONAS
for the Joint Research Project (015MD0-081). M.F.Z. Kadir received
funding from the Malaysian Ministry of Higher Education (MOHE)
for the Fundamental Research Grant Scheme (FRGS) (FP080-2022).
Declarations
Ethical approval Not applicable.
Competing interests The authors declare no competing interests.
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