International Journal of

Molecular Sciences

Article
Development of Polymer Blend Electrolyte
Membranes Based on Chitosan: Dextran with High
Ion Transport Properties for EDLC Application
Shujahadeen B. Aziz 1,2, * , Muhamad H. Hamsan 3 , Mohd F. Z. Kadir 3 , Wrya O. Karim 4 and
Ranjdar M. Abdullah 1
1 Advanced Polymeric Materials Research Lab., Department of Physics, College of Science, University of
Sulaimani, Qlyasan Street, Sulaimani 46001, Kurdistan Regional Government, Iraq
2 Komar Research Center (KRC), Komar University of Science and Technology, Sulaimani 46001, Kurdistan
Regional Government, Iraq
3 Centre for Foundation Studies in Science, University of Malaya, Kuala Lumpur 50603, Malaysia
4 Department of Chemistry, College of Science, University of Sulaimani, Qlyasan Street, Sulaimani 46001,
Kurdistan Regional Government, Iraq
* Correspondence: shujahadeenaziz@gmail.com




Received: 20 May 2019; Accepted: 5 July 2019; Published: 9 July 2019


Abstract: Solid polymer blend electrolyte membranes (SPBEM) composed of chitosan and dextran
with the incorporation of various amounts of lithium perchlorate (LiClO4 ) were synthesized.
The complexation of the polymer blend electrolytes with the salt was examined using FTIR
spectroscopy and X-ray diffraction (XRD). The morphology of the SPBEs was also investigated
using field emission scanning electron microscopy (FESEM). The ion transport behavior of the
membrane films was measured using impedance spectroscopy. The membrane with highest LiClO4
content was found to exhibit the highest conductivity of 5.16 × 10−3 S/cm. Ionic (ti ) and electronic
(te ) transference numbers for the highest conducting electrolyte were found to be 0.98 and 0.02,
respectively. Electrochemical stability was estimated from linear sweep voltammetry and found to be
up to ~2.3V for the Li+ ion conducting electrolyte. The only existence of electrical double charging at
the surface of electrodes was evidenced from the absence of peaks in cyclic voltammetry (CV) plot.
The discharge slope was observed to be almost linear, confirming the capacitive behavior of the EDLC.
The performance of synthesized EDLC was studied using CV and charge–discharge techniques.
The highest specific capacitance was achieved to be 8.7 F·g−1 at 20th cycle. The efficiency (η) was
observed to be at 92.8% and remained constant at 92.0% up to 100 cycles. The EDLC was considered
to have a reasonable electrode-electrolyte contact, in which η exceeds 90.0%. It was determined that
equivalent series resistance (Resr ) is quite low and varies from 150 to 180 Ω over the 100 cycles. Energy
density (Ed ) was found to be 1.21 Wh·kg−1 at the 1st cycle and then remained stable at 0.86 Wh·kg−1
up to 100 cycles. The interesting observation is that the value of Pd increases back to 685 W·kg−1 up
to 80 cycles.

Keywords: biopolymer electrolyte membranes; XRD analysis; FTIR study; Morphology; Impedance
study; EDLC fabrication

1. Introduction
Electrochemical capacitors are classified into three types: Pseudocapacitor, electrical double-layer
capacitor (EDLC), and hybrid capacitor [1]. In pseudocapacitor, Faradaic process is involved as the
energy storage mechanism with metal oxide and conducting polymer electrodes [2]. However, in EDLC,
which is usually composed of two identical carbon-based electrodes, non-Faradaic process is envolved

Int. J. Mol. Sci. 2019, 20, 3369; doi:10.3390/ijms20133369 www.mdpi.com/journal/ijms

Int. J. Mol. Sci. 2019, 20, 3369 2 of 26

during the charge storage process, where the accumulation of charge at the double-layer occurs on
the surface of carbon-based electrodes [3]. In the third type, i.e., in the hybrid capacitor, the energy
storage mechanism is based on the combination of EDLC and pseudocapacitor, i.e., both Faradaic
and non-Faradaic processes contribute. Among these capacitors, EDLC has shown to obtain through
a straightforward fabrication process. Moreover, EDLC possesses valuable properties, such as long
life cycle, high power density and light in weight [4]. In making such capacitor, activated carbon has
been reported to be compatible with polymer electrolyte [5–7]. Several features of activated carbon,
for instance, high surface area, high electrical conductivity, cost-effectiveness, and excellent chemical
stability, make it preferable for EDLC applications [8].
Biopolymers are preferable over non-degradable synthetic polymers as host polymers in polymer
electrolyte system because of their renewability, biocompatibility, and biodegradability [9,10]. They are
usually extracted from natural resources, e.g., cellulose from plants [11], starches from potato, maize
and cassava [12], chitosan from crustacean animals [13], carrageen from seaweed [14], and dextran from
bacteria [15]. The last one is obtained by growing cultures of bacteria called Leuconostocmesenteroides
in a medium filled with sucrose. Dextransucrase as an enzyme is excreted in the medium where
excess sucrose had converted to dextran [16]. Dextran with 1,6-α-d-glucopyranosidic linkages is a
biodegradable and a non-toxic polymer in the polymer backbone [17]. Regarding the backbone of
dextran, it is clear to observe two main functional groups, such as hydroxyl and glycosidic bond, which
possess electron lone pairs that contribute in the ionic conduction [18]. Herein, it is interesting that
chitosan as one of the derivatives of amino polysaccharides called chitin produced from exoskeleton of
crustaceans or insects. Both amine and hydroxyl functional groups enable chitosan to serve as one of
ionic conductors [19].
Blending two or more polymers has motivated researchers to improve the characteristics of
individual polymers. Hamsan et al. [20] have showed that potato starch-methylcellulose blend
film is more amorphous in structure than both pure methylcellulose film and potato starch film.
It is well-known that the amorphous region in polymer electrolyte is mainly responsible for ionic
conduction [21]. As concluded in the report published by Tamilselvi and Hema [22], mechanical
properties or structure stability of a material can be manipulated by polymer blending method. Blended
polymer composites provide more sites for ionic complexation process to occur, which makes ionic
conduction to be efficient than single polymer [23]. Based on our previous work [24], in 60 wt.%
chitosan and 40 wt.% dextran blend system, the amorphous structure was shown to be dominant.
Therefore, in this work, a similar percentage of chitosan and dextran has been blended along with
incorporation of lithium perchlorate (LiClO4 ). In addition to that, thehighest relatively conducting
electrolyte has also been used as electrode separators in the EDLC.

2. Results and Discussion

2.1. Structural (XRD and FTIR) Analysis

XRD analysis was carried out on pure CS, CS:Dextran and CS:Dextran: LiClO4 systems at the
ambient temperature. In our previous work, it was shown that pure CS exhibits several crystalline
peaks at 2θ = 15.1, 17.7, and 20.9◦ [25,26], as shown in Figure 1a, whereas Dextran exhibited two
hollows at 2θ = 18 and 23◦ [27]. In the present work, the XRD pattern of CS:Dextran showed two
hollows and no crystalline peaks can be observed, as can be seen in Figure 1b. These broad hollows
indicate that a fully amorphous structure has been formed [28]. Earlier reports documented that a
broad diffraction peaks corresponds to amorphous nature of the polymer electrolyte [29,30]. In the
current study, it has been found that the intensity of the hump of CS:Dextrandecreases in the intensity
with the addition of LiClO4 salt and broad nature also increases, as shown in Figure 2a,b. It is clear that
at 20 wt.% of the salt some new peaks appeared, which are due to polymer slat complexes rather than
pure salt. Interestingly, at 40 wt.% of the added salt, these new peaks disappeared and the intensity
of the hump decreased. The results obtained here confirm the amorphous nature of the polymer
Int. J. Mol. Sci. 2019, 20, x 3 of 26
Int. J. Mol. Sci. 2019, 20, 3369 3 of 26
diffusivity
Int. and 20,
J. Mol. Sci. 2019, high
x ionic conductivity. No peaks corresponding to pure LiClO4 appeared 3inofthe 26
CS:Dextran blend polymer electrolyte, which indicates the complete dissociation of the dopant salt
electrolytes.
in the polymer
diffusivity andThe amorphous
blend
high matrix.
ionic nature provides
conductivity. greater
No peaks ionic diffusivity
corresponding and LiClO
to pure high ionic conductivity.
4 appeared in the
No peaks corresponding
CS:Dextran blend to pure LiClO appeared in the CS:Dextran blend polymer electrolyte,
polymer electrolyte,4 which indicates the complete dissociation of the dopant which
salt
180
indicates the
in the polymer blendcomplete dissociation
160 matrix.
of the dopant salt in the polymer blend matrix.
17.2o (a)
140 20.9o
(a.u) (a.u) 180 15.1 o
120
160 17.2o
100 (a)
Intensity

140 20.9o
80 15.1 o
120
60
100
Intensity

40
80
20
60
0
40
10 20 30 40 50 60 70 80
20
0 2θ degree
10 20 30 40 50 60 70 80
500
2θ degree
400 (b)
(a.u) (a.u)

500
300
Intensity

400 (b)
200
300
Intensity

100
200
0
100 10 20 30 40 50 60 70 80

0 2θ degree
10 20 30 40 50 60 70 80
2θ degree
Figure 1.the XRD pattern for (a) pure CS and (b) CS:Dextran blend film.
Figure 1. The XRD pattern for (a) pure CS and (b) CS:Dextran blend film.
Figure 1.the XRD pattern for (a) pure CS and (b) CS:Dextran blend film.
500

400 (a)
(a.u) (a.u)

500
300
Intensity

400 (a)
200
300
100
Intensity

200
0
100 10 20 30 40 50 60 70 80

0 2θ degree
10 20 30 40 50 60 70 80
2θ degree
500

400 (b)
(a.u) (a.u)

500
300
Intensity

400 (b)
200
300
Intensity

100
200
0
100 10 20 30 40 50 60 70 80

0 2θ degree
10 20 30 40 50 60 70 80
Figure 2. The XRD pattern for (a) CSDPB2 and (b) CSDPB4 blend electrolytes.
2θ degree
Figure 3a–cFigure
shows2.the
the XRD
FTIRpattern
spectrafor (a) CSDPB2 and (b) CSDPB4 blend electrolytes.
of the pure CS:Dextran and blend electrolyte films at three
separate regions. Fourier transform infrared (FTIR) spectroscopy has been widely used by many
Figure 2.the XRD pattern for (a) CSDPB2 and (b) CSDPB4 blend electrolytes.
Int. J. Mol. Sci. 2019, 20, x 4 of 26

Figure 3a–c shows the FTIR spectra of the pure CS:Dextran and blend electrolyte films at three
Int. J. Mol. Sci. 2019, 20, 3369 4 of 26
separate regions. Fourier transform infrared (FTIR) spectroscopy has been widely used by many
researchers in dealing with the formation of polymer blends. FTIR spectroscopy provides insight
into intermolecular
researchers in dealing interaction
with thethroughformation analysis of FTIRblends.
of polymer spectra FTIR
on thespectroscopy
basis of stretching
provides or bending
insight
vibrations
into of particular
intermolecular bonds. The
interaction mainanalysis
through characteristic
of FTIRbands
spectrain the
on thespectra
basisofofdextran
stretching were or found
bending at
1146 and 1021 cm −1. The band peak at 1086 cm–1 is assigned to both valent vibrations of C–O–C bond
vibrations of particular bonds. The main characteristic bands in the spectra of dextran were found at
and glycosidic
1146 and 1021 cm −1 . The
bridge. The bandpresence
peak atof1086 cm–1atis1021
a peak cm–1 belongs
assigned to the vibrations
to both valent high chainofflexibility
C–O–C bond that
present
and in dextran
glycosidic around
bridge. The the glycosidic
presence bonds
of a peak at[31].
1021Forcm–1 CS:Dextran,
belongs to the the FT-IR spectrum
high chain exhibited
flexibility that
the presence
present in dextran of OHaroundgroups that couldbonds
the glycosidic be confirmed by the appearance
[31]. For CS:Dextran, the FT-IR of broad band
spectrum exhibitedwiththea
maximum
presence of at
OH 3351cm
groups −1[32,33]. In a comparison, the band peaked at 2906 cm−1 can be attributed to
that could be confirmed by the appearance of broad band with a maximum at
3351cm −1 [32,33].
C–H stretching in In
dextran [32,33], since
a comparison, suchpeaked
the band band was not cm
at 2906 −1 can be
observed in the FTIR spectra
attributed to C–Hofstretching
chitosan
[34].
in The peak
dextran at 1000
[32,33], sincecm suchcharacterizes
−1
band was notthe significant
observed chain
in the FTIR flexibility
spectra of exist in dextran
chitosan [34]. Thearoundpeaktheat
1000 cm−1 characterizes
glycosidic bond [32]. The theC–H bendingchain
significant usually appeared
flexibility existatin1450 cm−1around
dextran , whereas thethe broad band
glycosidic bondstarts
[32].
at 1158
The C–Hcm bending usually appeared at 1450 cm−1 , whereas
−1, indicating asymmetrical –C–O–C– stretching
the of the band
broad ring [33].
startsThe cm−1
sharp
at 1158 peak at 1009
, indicating
cm and small–C–O–C–
−1
asymmetrical one at 1067 cm isofascribed
stretching −1
the ringto the The
[33]. existence
sharp of peakC–O at bands
1009 cm −1
[34].andWith increasing
small one at
LiClO4
1067 cm−1 salt, these peaks
is ascribed to theare becomes
existence distinguishable,
of C–O bands [34]. as Withobserved
increasing in LiClO4
our previous
salt, these work for
peaks
chitosan-based
are electrolyte. ForasC-H
becomes distinguishable, configuration
observed in dextran,
in our previous work a characteristic
for chitosan-based peak appeared
electrolyte. at For
615
cm−1[35].
C-H For both stretching
configuration in dextran, vibrations of the C–O–C
a characteristic peak appeared 615 cm−1 bridge
bond andatglycosides [35]. For a peak
bothcentered
stretching at
1155 cm −1. Two peaks centered at 1651 cm−1 and 1554 cm−1 corresponding
vibrations of the C–O–C bond and glycosides bridge a peak centered at 1155 cm . Two peaks centered −1 to carboxamide
at 1651 cm−1 and 1554
(O=C–NHR) amine −1 corresponding
cm(NH2) bands, respectively [34]. It (O=C–NHR)
to carboxamide is interestingand to amine
observe(NH2) that abands,
shift
occurred in [34].
respectively the Itcarboxamide
is interesting (O=C–NHR)
to observe thatand amine
a shift (NHin
occurred 2) the
bands which strongly
carboxamide (O=C–NHR) confirms
and
complexation between chitosan: Dxetran and the dopant salt. In
amine (NH2 ) bands which strongly confirms complexation between chitosan: Dxetran and the dopant fact, this attachment of cation salt to
nitrogen
salt. In fact,andthisoxygen atoms of
attachment cancation
reducesaltthe
to vibration
nitrogen and intensity
oxygen of atoms
the N–H can or O=C–NHR
reduce bonds
the vibration
owing to the higher molecular weight after cation binding and
intensity of the N–H or O=C–NHR bonds owing to the higher molecular weight after cation binding eventually resulted in shifting and
lowering
and eventually in intensity
resulted[36]. More interesting
in shifting and lowering observation
in intensityis[36].
the More
incorporation
interesting ofobservation
LiClO4 saltisinto the
CS:Dextran resulting
incorporation of LiClO in4 asalt
greatintochange in the resulting
CS:Dextran intensity in of athe bands.
great changeThisinchange in intensity
the intensity of theofbands.
these
bands
This is strongly
change related
in intensity of to thebands
these alterations in therelated
is strongly macromolecular order.inThese
to the alterations bands in the spectra
the macromolecular order.
of the bands
These complexes in themay result
spectra offrom more and may
the complexes less ordered structures
result from more and [37].less ordered structures [37].

pekas due to C-H (b) (c)

configuration (a)
bands due to
(v) bands due to C-
C-H bending bands due to O=C broad band due to H stretching
and NH2 groups v OH groups
(v)

(iv)
(iv)
(iv)

(iii)
Transm ittance (a.u)%

Transmitance (a.u) %
Transmitance (a.u) %

(iii)
(iii)

(ii)

(ii)
(ii)
(i)

(i)

pekas due to C-O-C bond (i)

peaks due to C-O bands

400 600 800 1000 1200 1300 1400 1500 1600 1700 1800 4000 3500 3000 2500
-1 -1 -1
Wavenumber (cm ) Wavenumber (cm ) Wavenumber (cm )

Figure
Figure 3. FTIRspectra
3.FTIR spectraof
of (i)
(i) CS:Dextran
CS:Dextran (pure
(pure film),
film), (ii)
(ii) CSDPB1,
CSDPB1, (iii)
(iii) CSDPB2,
CSDPB2, (iv)
(iv) CSDPB3,
CSDPB3, andand (v)
(v)
CSDPB4 −1 −1 −1 −1 −1
CSDPB4 in in the
the region
region(a)
(a)700700cm
cm−1 to
to1300
1300cm
cm−1,, (b)
(b) 1400
1400cm
cm−1 to
to 1800
1800cm
cm−1,, and
and (c)
(c) 3000
3000cm
cm−1 to
to
3800 cm −1 .
3800 cm .
−1
Int. J. Mol. Sci. 2019, 20, 3369 5 of 26
Int. J. Mol. Sci. 2019, 20, x 5 of 26

2.2.
2.2.Morphological
MorphologicalStudy
Study
Dealing
Dealingwith withmaterial
materialsurface
surfaceisisvital
vitaltotounderstand
understandthe thestructural
structuralchanges
changesover overa anumber
numberofof
processes.
processes. Recent studies revealed that the morphology aspect in polymers provides someinsights
Recent studies revealed that the morphology aspect in polymers provides some insights
into
intothe
thechanges
changesininstructural
structuralororelectrical
electricalproperties
properties[9,25,28].
[9,25,28].Polymer
Polymerfamilyfamilycancanbebecategorized
categorizedinin
terms
termsofofcrystallinity
crystallinity into
intocrystallineand
crystallineand amorphous
amorphous polymers.
polymers.On Onthe the
one one
hand, polymer
hand, crystals
polymer are
crystals
characterized by compact assembly of stereo-regular chains and thereby
are characterized by compact assembly of stereo-regular chains and thereby exhibit high modulus exhibit high modulus and
hardness, but weak
and hardness, but toughness.
weak toughness.On theOn other
thehand,
other amorphous polymers
hand, amorphous featuresfeatures
polymers are rubbery or glassyor
are rubbery
inglassy
behavior [38]. In our previous work, SEM technique was used to study the
in behavior [38]. In our previous work, SEM technique was used to study the compatibility compatibility of salts withof
polar polymers [39]. Figure 4a–d shows the FESEM images for a number
salts with polar polymers [39]. Figure 4a–d shows the FESEM images for a number of the CS:Dextranof the CS:Dextran systems
incorporated with various
systems incorporated with weight
variouspercentage of LiClO4 salt.
weight percentage The surface
of LiClO morphologies
4 salt. The of the blendof
surface morphologies
electrolyte samples are almost smooth and there are no protruded particles
the blend electrolyte samples are almost smooth and there are no protruded particles on the on the sample surfaces.
sample
This was observed
surfaces. This wasinobserved
our previousin our work [40] where,
previous as more
work [40] saltas
where, is more
added, more
salt particles
is added, moreprotruded
particles
out of the surface.
protruded out of This indicates
the surface. that
This polymerthat
indicates matrix capacity
polymer is limited
matrix capacity to is
accommodate excess salt,
limited to accommodate
which in turn led to salt recrystallization. It is apparent, as recrystallization proceeds,
excess salt, which in turn led to salt recrystallization. It is apparent, as recrystallization proceeds, the amount the
ofamount
free ionsof lowers,
free ions which
lowers, results
whichin results
conductivity value decrement
in conductivity [41]. In fact,
value decrement [41].the
Insmooth
fact, thesurface
smooth
ofsurface
the samples
of the indicates that the complexation
samples indicates had takenhad
that the complexation place among
taken placethe polymer
among the blends
polymer and the
blends
incorporated LiClO
and the incorporated 4 salt. The data results of the present work indicate that polymer
LiClO4 salt. The data results of the present work indicate that polymer blend blend fabrication
isfabrication
a novel approach
is a noveland straightforward methodology with
approach and straightforward high DC conductivity.
methodology with highThe DCoccurrence of
conductivity.
the
Theextent of complexation of the dopant salt and CS:Dextran was realized from the FTIR study.

(a)

Figure 4. Cont.
Int. J. Mol. Sci. 2019, 20, 3369 6 of 26
Int. J. Mol. Sci. 2019, 20, x 6 of 26

(b)

(c)

Figure 4. Cont.
Int. J. Mol. Sci. 2019, 20, 3369 7 of 26
Int. J. Mol. Sci. 2019, 20, x 7 of 26

(d)

Figure4. FESEM
Figure 4.FESEM images
images forCSDPB1,
for (a) (a) CSDPB1, (b) CSDPB2,
(b) CSDPB2, (c) and
(c) CSDPB3, CSDPB3, and (d)
(d) CSDPB4 CSDPB4
blend blend
electrolytes.
electrolytes.
2.3. Impedance Study
2.3.A
Impedance Study
comparably new and powerful technique in the characterization of a number of the electrical
properties of electrolyte
A comparably newmaterials and the
and powerful interfaceinregion
technique with electronically
the characterization conducting
of a number electrodes
of the electrical
isproperties
electrochemical impedance spectroscopy [28,42,43]. The impedance plot for
of electrolyte materials and the interface region with electronically conducting electrodes CS:Dextran–LiClO 4
polymer blend electrolyte
is electrochemical impedance systems at room temperature
spectroscopy [28,42,43]. The are impedance
shown in Figureplot for5a–d. The complex 4
CS:Dextran–LiClO
impedance
polymer blendplots electrolyte
reveal two systemsmain distinct
at roomregions: The semicircle
temperature are shown observed
in Figureat the highThe
5a–d. frequency
complex
region, which is due to the bulk character of the electrolytes, and the linear
impedance plots reveal two main distinct regions: The semicircle observed at the high frequency region at the low frequency
range, which
region, which is attributed
is due to to thethebulk
blocking electrodes
character of the[42,44,45]. The and
electrolytes, membrane electrolytes
the linear region at carry
the ion
low
carriers,
frequencyandrange,
thus, ion
which diffusion occurstothrough
is attributed the membrane
the blocking electrodesas[42,44,45].
an AC electric field is applied,
The membrane and
electrolytes
consequently, ion accumulation
carry ion carriers, and thus, ionbuilds up atoccurs
diffusion the electro/electrolyte
through the membrane interface.as Due
an AC to the electronic
electric field is
nature of the
applied, andstainless steel electrodes,
consequently, ions cannot
ion accumulation cross
builds upthe system,
at the and thus, the real
electro/electrolyte and imaginary
interface. Due to the
parts of the nature
electronic impedance of thecan be measured
stainless at various
steel electrodes, frequencies,
ions cannot cross which resultedand
the system, in impedance
thus, the real plots.
and
Itimaginary
is interesting that, at the intermediate frequencies, certainly at −45
parts of the impedance can be measured at various frequencies, which resulted in ~ inclined lines indicate the
occurrence
impedanceofplots.Warburg It isimpedance
interestingasthat,a consequence of diffusion
at the intermediate of ions to certainly
frequencies, the electrode surface
at −45 [46].
~ inclined
Furthermore, the spike feature at the low frequency region is a characteristic
lines indicate the occurrence of Warburg impedance as a consequence of diffusion of ions to of diffusion process [29].
the
Itelectrode
is apparent, in Figure
surface 5 that, with increasing
[46]. Furthermore, the spikesalt concentration,
feature at the low the bulk resistance
frequency region is(see the insets)
a characteristic
decreased.
of diffusionThe Rb value
process [29].is It
determined
is apparent, byinthe point5where
Figure that, withthe semicircle
increasingintersects the real axis
salt concentration, the(Zr).
bulk
The equation below has been applied to determine the sample conductivity
resistance (see the insets) decreased. The Rb value is determined by the point where the based on the R value and
b semicircle
the sample dimensions:
intersects the real axis (Zr). The equation below !   has been applied to determine the sample
conductivity based on the Rb value and the sample t
1 dimensions:
σdc = × (1)
Rb A
 1  t 
σ dc =   ×   (1)
 Rb   A 
In the above equation, the polymer electrolyte film thickness and the film surface area are,
respectively, denoted by t and A. Table 1 shows the calculated DC conductivity for all the samples.
The high DC conductivity of blend electrolytes is a guarantee for EDLC application. To get more
information about the charge transfer resistance of the samples Bode plots were also studied. More
insights about the electrical properties of the blend electrolyte samples can be grasped from the
 Int. J. Mol. Sci. 2019, 20, x 8 of 26

modeling of the impedance plots using electrical equivalent circuits (EECs). Through the modeling
Int. J. Mol. Sci. 2019, 20, 3369 8 of 26
of impedance plots, it is possible to estimate the bulk resistance and circuit elements.

(a)
7

7
Zi (Ohm) x 10 5
7
Rb =3.8 x 10 Ohm
4

0
0 2 4 6 8
7
Zr (Ohm) x 10

14
(b)
12

10

4
Rb = 7 x 10 Ohm
4
Zi (Ohm) x 10

0
0 2 4 6 8 10 12 14
4
Zr (Ohm) x 10

Figure 5. Cont.
Int. J. Mol. Sci. 2019, 20, 3369 9 of 26
Int. J. Mol. Sci. 2019, 20, x 9 of 26

(c)
6

3
Zi (Ohm) x 10
4

2
3
Rb = 1.5 x 10 Ohm
1

0
0 1 2 3 4 5 6 7
3
Zr (Ohm) x 10

1400

(d)

1200

1000

800
Zi (Ohm)

600

400 Rb = 34 Ohm

200

0
0 200 400 600 800 1000 1200 1400
Zr (Ohm)

Figure 5. Cont.
Int. J. Mol. Sci. 2019, 20, 3369 10 of 26
Int. J. Mol. Sci. 2019, 20, x 10 of 26

450

(e)
400

350

300
Zi (Ohm)

250

200

150
Rb = 3.7 Ohm

100

50

0
0 50 100 150 200 250 300 350 400 450
Zr (Ohm)

Figure 5. Experimental Impedance plots for (a) pure CS:Dextran film (b) CSDPB1, (c) CSDPB2, (d)
Figure 5.Experimental
CSDPB3, and (e) CSDPB4Impedance plots for
blend electrolyte (a) pure CS:Dextran film (b) CSDPB1, (c) CSDPB2, (d)
films.
CSDPB3, and (e) CSDPB4 blend electrolyte films.
In the above equation, the polymer electrolyte film thickness and the film surface area are,
Moreover,
respectively, the results
denoted of Nyquist
by t and A. Tableplots are further
1 shows established
the calculated DC by the consideration
conductivity of Bode
for all the plot.
samples.
From
The theDC
high electrochemical
conductivity viewpoint, Bode plotsisare
of blend electrolytes principallyfor
a guarantee helpful
EDLC inapplication.
understanding To the
get charge
more
transfer process in electrolyte materials [47].Figure 6 shows the Bode plots for
information about the charge transfer resistance of the samples Bode plots were also studied. More the pure CS:Dextran
blend film
insights andthe
about blend electrolyte
electrical films atofambient
properties temperature.
the blend electrolytePrevious
samples studies
can be have demonstrated
grasped from the
that three distinguished regions should be recognized from the Bode plots, which
modeling of the impedance plots using electrical equivalent circuits (EECs). Through the modeling of are capacitive,
diffusion, plots,
impedance and charge transfer
it is possible to regions
estimate[39,47–49]. Usually,and
the bulk resistance the circuit
capacitive region (namely plateau
elements.
region) can be observed at a very low frequency; from 10 to 100 Hz. However, this region could not
−2

be examined inDC
Table 1. this study, owing
conductivity to CS:Dex
for pure the frequency
and blendlimitations of the
electrolyte films measuring
at room equipment. As
temperature.
described in the impedance plots of Figure 5, the semicircle has been correlated to the ion transfer in
Sample Designation DC Conductivity (S/cm)
amorphous phase of electrolytes and the tails were related to the contribution of Warburg or
diffusion of ions, and therefore, CS:Dex
their accumulation at the 5.01 × 10−10
electrode/electrolyte interface [40,43,45].
CSDPB1 2.73 −7
× 10will
The ion accumulation on both sides of the electrolyte membrane produce electrical double layer
CSDPB2 1.27 × 10−5
capacitances. The results clearly indicated that, with increasing −4
CSDPB3
salt concentration, from 10 to 40
5.62 × 10
wt.%, the Warburg contribution CSDPB4(tail regions) has been increased,
5.16 × 10 −3 and therefore, the resistance
decreased due to the large amount of carrier density. It is obvious from Figure 6a that pure
CS:Dextran films show high charge transfer resistance. Obviously, the charge transfer resistance
Moreover, the results of Nyquist plots are further established by the consideration of Bode plot.
decreases with increasing salt concentrations as shown in Figures 6c and 6b. From Figures 5 and 6, it
From the electrochemical viewpoint, Bode plots are principally helpful in understanding the charge
is clear that the sample incorporated with 40 wt.% of LiClO4 exhibits the lowest resistance and thus a
transfer process in electrolyte materials [47]. Figure 6 shows the Bode plots for the pure CS:Dextran
high conductivity resulted.
blend film and blend electrolyte films at ambient temperature. Previous studies have demonstrated
that three distinguished regions should be recognized from the Bode plots, which are capacitive,
diffusion, and charge transfer regions [39,47–49]. Usually, the capacitive region (namely plateau region)
can be observed at a very low frequency; from 10−2 to 100 Hz. However, this region could not be
examined in this study, owing to the frequency limitations of the measuring equipment. As described
in the impedance plots of Figure 5, the semicircle has been correlated to the ion transfer in amorphous
phase of electrolytes and the tails were related to the contribution of Warburg or diffusion of ions, and
therefore, their accumulation at the electrode/electrolyte interface [40,43,45]. The ion accumulation on
both sides of the electrolyte membrane will produce electrical double layer capacitances. The results
Int. J. Mol. Sci. 2019, 20, 3369 11 of 26

clearly indicated that, with increasing salt concentration, from 10 to 40 wt.%, the Warburg contribution
(tail regions) has been increased, and therefore, the resistance decreased due to the large amount of
carrier density. It is obvious from Figure 6a that pure CS:Dextran films show high charge transfer
resistance. Obviously, the charge transfer resistance decreases with increasing salt concentrations as
shown in Figure 6b,c. From Figures 5 and 6, it is clear that the sample incorporated with 40 wt.% of
Int. J. Mol.
LiClO4 Sci. 2019,the
exhibits 20, lowest
x resistance and thus a high conductivity resulted. 11 of 26

1,400,000.00

1,200,000.00
(a)
1,000,000.00
(Ohm)

800,000.00
2
|Z|x10

600,000.00

400,000.00

200,000.00

0.00
100.00 1,000.00 10,000.00 100,000.00 1,000,000.00
Frequency (Hz)

1200

1000 (b) CSDPB1

(Ohm)

800 CSDPB2
2

600
|Z|x10

400

200

0
100.00 1,000.00 10,000.00 100,000.00 1,000,000.00
Frequency (Hz)

9
8 CSDPB3
(c)
7
(Ohm)

6 CSDPB4
5
2
|Z|x10

4
3
2
1
0
100.00 1,000.00 10,000.00 100,000.00 1,000,000.00
Frequency (Hz)

Figure 6. Bode plots for (a) pure CS:Dextran film (b) CSDPB1 and CSDPB2, and (c) CSDPB3, and
Figure 6.Bode
CSDPB4 plots for (a)
blend electrolyte pure CS:Dextran film (b) CSDPB1 and CSDPB2, and (c) CSDPB3, and
films.
CSDPB4 blend electrolyte films.
The EECs model can be usually utilized for fitting, i.e., it can be used in the analysis of impedance
Table
spectroscopy, 1.DCthe
since conductivity
model isfor pure CS:Dex and quick,
straightforward, blend electrolyte films ataroom
and provides temperature.
complete picture of the
system [50]. The acquired impedance plots can be interpreted with respect to the equivalent circuit
DC Conductivity
SampleinDesignation
including Rb for the charge carriers the sample and two constant phase elements (CPE), as presented
(S/cm)
in the insets of Figure 7a. The high frequency
CS:Dex region shows 5.01 the combination
× 10−10 of Rb and CPE, whilst the
low frequency region exhibits CPE,CSDPB1
i.e., the developed double layer capacitance
2.73 × 10 − 7 between the electrodes
CSDPB2 1.27 × 10−5
CSDPB3 5.62 × 10−4
CSDPB4 5.16 × 10−3
The EECs model can be usually utilized for fitting, i.e., it can be used in the analysis of
impedance spectroscopy, since the model is straightforward, quick, and provides a complete picture
 Int. J. Mol. Sci. 2019, 20, x 12 of 26

whilst the low frequency region exhibits CPE, i.e., the developed double layer capacitance between
the electrodes and SPE. The abbreviated term CPE is more commonly used in the equivalent circuit
Int. J. Mol.than
rather Sci. 2019,
as an20,ideal
3369 capacitor in real system. This is due to the fact that the behavior of the12actual
of 26
SPE is varied from that of an ideal capacitor considered in a pure semicircular pattern [51]. As
discussed above, Warburg impedance at −45 ~ inclined lines are definitely a consequence of
and SPE. The abbreviated term CPE is more commonly used in the equivalent circuit rather than as an
diffusion of ions to the electrode surface. In this report, the depressed semicircle has been explained
ideal capacitor in real system. This is due to the fact that the behavior of the actual SPE is varied from
by CPE instead of a capacitor [52]. The impedance of ZCPE can be written as [53,54]:
that of an ideal capacitor considered in a pure semicircular pattern [51]. As discussed above, Warburg
impedance at −45 ~ inclined lines are definitely cos(πna/ consequence
2) sin(πnof
/ 2diffusion
) of ions to the electrode
Z CPE = − explained
j (2)
surface. In this report, the depressed semicircle hasn been
Ymω Ymω
n by CPE instead of a capacitor [52].
The impedance of ZCPE can be written as [53,54]:
where Ym refers to the CPE capacitance, ω is the angular frequency and n is associated to the
deviation of the vertical axis of Z
the plot cos πn/2
in (the )
complexsin(πn/2)
CPE = − j impedance plots. Finally, the real (Zr) and
(2)
Y m ωn
imaginary (Zi) values of complex impedance (Z*) related Ym ωwith
n
the equivalent circuit (insets of
Figure
where Y 7a) can be
refers expressed
to the as:
CPE capacitance, ω is the angular frequency and n is associated to the deviation
m
of the vertical axis of the plot in the complex
R1 + R12Y1impedance
ω n1 cos(πn1plots.
/ 2) Finally,cos(
the real (Zr ) and imaginary
πn2 / 2)
(Zi ) values of complex = Rs +
Z r impedance (Z*) related with the equivalent +
circuit (insets of Figure 7a) can (3)
be
expressed as: 1 + 2 R1Y1ω cos(πn1 / 2) + R1 Y1 ω
n1 2 2 2 n1
Y2ω n2
R1 + R21 Y1 ωn1 cos(πn1 /2) cos(πn2 /2)
Zr = Rs + R 2
Y ω n1
sin( π n / 2 ) +sin(πn n/ 2)
Y2 ω2 2
(3)
Z i = 1 + 2R1 Y11nω1 1 cos(πn1 /21 ) + R Y ω 1+
n 2 2 2n
1 1 (4)
1 + 2 R1Y1ω 1
n1 πn1 / 2) + R1 Y1 ω
cos(2 2 2n n 1
Y2ω 2
2 R1 Y1 ω sin(πn1 /2) sin(πn2 /2)
Zi = + (4)
1 + 2R1 Y1 ωn1 cos(πn1 /2) + R21 Y12 ω2n1 Y2 ωn2

7000
Experimental
(a)
fitting
6000

5000

4000
Zi (Ohm)

3000

2000

1000

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Zr (Ohm)

Figure 7. Cont.
Int. J. Mol. Sci. 2019, 20, 3369 13 of 26
Int. J. Mol. Sci. 2019, 20, x 13 of 26

Figure 7. Experimental Impedance and fitting (EEC) plots for (a) CSDPB2 and (b) CSDPB4 blend
Figure 7.Experimental Impedance and fitting (EEC) plots for (a) CSDPB2 and (b) CSDPB4 blend
electrolyte films.
electrolyte films.

All circuit element parameters that are used for fitting the experimental impedance plots for all the
All circuit element parameters that are used for fitting the experimental impedance plots for all
selected samples are presented in Table 2. These elements are exactly related to the parameters in the
the selected samples are presented in Table 2. These elements are exactly related to the parameters in
above equations, such that Yo corresponds to Ym , N corresponds to n1 and n2 according to CPE1 and
the above equations, such that Yo corresponds to Ym, N corresponds to n1 and n2 according to CPE1
CPE2 elements and R corresponds to R1 . In the Cole–Cole plot, the semicircle disappears at a certain
and CPE2 elements and R corresponds to R1. In the Cole–Cole plot, the semicircle disappears at a
high salt concentration of the salt (see Figure 7b), suggesting that only the resistive component of the
certain high salt concentration of the salt (see Figure 7b), suggesting that only the resistive
polymer prevails [55]. In this case, the values of Zr and Zi associated to the EEC can be expressed as:
component of the polymer prevails [55]. In this case, the values of Zr and Zi associated to the EEC can
be expressed as: cos(πn/2)
Zr = R + (5)
Ym ω
cos( πn / 2)
n
Zr = R + (5)
sin(πn/2Ymω) n
Zi = (6)
Ym ωn
sin(πn / 2)
Zi = (6)
Table 2. ofmω
The parameters of the circuit elements Y then selected blend electrolyte membranes at
ambient temperature.

Table Sample R1 /Ohm

2.The parameters Y 1 elements nof
of the circuit 1 the selected Y 2 /nMho
Rs blend n2
electrolyte membranes at
ambient temperature. 696
CSDPB2 619 pMho 0.9345 805 984 0.99
CSDPB4 3.56 27 µMho 0.817 - - -
Sample R1/Ohm Y1 n1 Rs Y2/nMho n2
CSDPB2
2.4. Transference 696
Number Measurement 619 pMho
(TNM) Study0.9345 805 984 0.99
CSDPB4 3.56 27 μMho 0.817 - - -
The ionic (ti ) and electronic (te ) transference number can be gained from the ratio of steady-state
current (Iss ) and initial current (Ii ). The value of ti can be calculated from the following equation [55]:
2.4. Transference Number Measurement (TNM) Study
The ionic (ti) and electronic (te) transference Ii − Iss can be gained from the ratio of steady-state
ti = number (7)
Ii be calculated from the following equation [55]:
current (Iss) and initial current (Ii). The value of ti can

− I time for the highest conducting electrolyte.

Figure 8 shows the polarization plot of currentI versus
t i = ofi bothssions and electrons. It is seen that the current
The current at initial time is large due to migration (7)
I
is decreased rapidly prior to achieving a constant valuei of 0.4 µA, since only electron can pass through
the stainless
Figure steel electrodes.
8 shows At steady state,
the polarization plot the
of cell is polarized
current versus as thefor
time current flow is stayed
the highest due
conducting
electrolyte. The current at initial time is large due to migration of both ions and electrons. It is seen
Int. J. Mol. Sci. 2019, 20, x 14 of 26

Int. J.the
that Mol.current
Sci. 2019,is20, 3369
decreased 14 of 26
rapidly prior to achieving a constant value of 0.4 μA, since only electron
can pass through the stainless steel electrodes. At steady state, the cell is polarized as the current
flow is stayed
to electron [56].dueThe toconstant
electron current
[56]. The constant
value current
indicates value
ionic indicates
conductor ionic conductor
behavior behavior
of the electrolyte of
[57],
the electrolyte [57], where I ss and Ii are observed to be at 0.4 and 27.8 μA, respectively. Therefore, ti
where Iss and Ii are observed to be at 0.4 and 27.8 µA, respectively. Therefore, ti and te transference
and
number te transference
for the electrolytenumber arefor thetoelectrolyte
found are
be 0.98 and found
0.02, to be 0.98
respectively. and
This 0.02, respectively.
confirms This
the fact that ion is
confirms the fact that ion is the dominant charge carrier in the electrolyte.
the dominant charge carrier in the electrolyte. Othman et al. [58] documented ti values from 0.93 Othman et al. [58]
to
documented
0.98 for poly methyl ti values from 0.93 (PMMA)-lithium
methacrylate to 0.98 for poly trifluoro
methyl methacrylate (PMMA)-lithium
methane sulfonate trifluoro
(LiCF3 SO3 ). Therefore,
methane sulfonate (LiCF
the high transference 3SO3). Therefore, the high transference number may be correlated with the
number may be correlated with the effect of polymer-ion and ion-ion interactions
effect of polymer-ion
on the microscopic parameter. and ion-ion interactions on the microscopic parameter.

40

35

30
Ii
25
Current (μA)

20

15

10 Iss

0
0 500 1000 1500 2000 2500
Time (s)

Figure 8. Polarization current versus time for the CSDPB4 blend electrolyte film.
Figure 8.Polarization current versus time for the CSDPB4 blend electrolyte film.
2.5. LSV Analysis
2.5. LSV Analysis
Determination of potential stability is an imperative characteristic of the polymer electrolyte for
energyDetermination
storage device of applications.
potential stability
Figureis an imperative
9 shows the LSVcharacteristic of the polymer
plot of the highest electrolyte
conducting (CSDPB4)for
energy storage device applications. Figure 9 shows the LSV plot of the highest conducting
electrolyte. It is noticeable that there is no current flowing below 2.3 V, which indicates that there is (CSDPB4)
electrolyte. It is noticeable
no electrochemical reactionthat there isbelow
occurring no current flowing below
this potential window. 2.3 The
V, which
increaseindicates that beyond
of current there is
no
2.3 electrochemical
V is related to the reaction occurring
decomposition of below this potential
the polymer window.
electrolyte, The the
signifying increase of current reaction
electrochemical beyond
2.3 V is related to the decomposition of the polymer electrolyte, signifying
within the polymer electrolyte [59]. Monisha et al. [60] stated that the threshold voltage is that the the electrochemical
reaction within
current flows the polymer
through electrolyte
the cells. Shukur et[59]. Monisha
al. [52] reportedet al. [60] stated that
a decomposition the threshold
voltage at 2.10 V voltage is
of lithium
that the current
salt based flows through
biopolymer the cells.
electrolyte. Thus,Shukur et al. [52]
the potential reported
stability, a decomposition
i.e., potential windowvoltage at 2.10 V
of the relatively
of lithium salt based biopolymer electrolyte. Thus, the potential stability,
high conducting electrolyte in this work is suitable for energy storage device applications. i.e., potential window of
the relatively high conducting electrolyte in this work is suitable for energy storage device
applications.
Int. J. Mol. Sci. 2019, 20, 3369 15 of 26
Int. J. Mol. Sci. 2019, 20, x 15 of 26

0.01

0.009

0.008
Current density (A/cm )
2
0.007

0.006

0.005

0.004

0.003
2.3 V
0.002

0.001

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

Figure 9. LSV plot for the highest conducting chitosan-dextran-LiClO4 (CSDPB4) sample.
Figure 9.LSV plot for the highest conducting chitosan-dextran-LiClO4 (CSDPB4) sample.
2.6. EDLC Study
2.6. EDLC Study
CV and EDLC Characteristics
CV and EDLC
Figure shows the cyclic voltammogram of the fabricated EDLC at a sweep rate of 10 mV·s−1 .
10 Characteristics
It canFigure
be observed
10 shows that
thethere
cyclicisvoltammogram
no peak withinof the
thepotential
fabricated range
EDLCof 0attoa sweep
1.0 V. However,
rate of 10 there
mV·s−1is.
It can be observed that there is no peak within the potential range of 0 to 1.0 V. However, therestated
an electrical double layer, i.e., non-Faradaic current at the surface of the electrodes [61]. As is an
previously, energy storage mechanism in EDLC goes via non-Faradaic, which
electrical double layer, i.e., non-Faradaic current at the surface of the electrodes [61]. As stated means that no redox
reaction process.
previously, energy The addition
storage of salt inin
mechanism the electrolyte
EDLC goes viaproduces positively
non-Faradaic, charged
which meansionthat
(i.e.,nocations)
redox
and negatively charged ions (i.e., anions). Once the EDLC is charged, cations
reaction process. The addition of salt in the electrolyte produces positively charged ion (i.e., and anions will cations)
migrate
to negative
and andcharged
negatively positiveions
electrodes, respectively.
(i.e., anions). Once theAt negative
EDLC electrode,
is charged, the and
cations induced
anionselectric field at
will migrate
the electrode attracts cations and repels anions, where the opposite action takes
to negative and positive electrodes, respectively. At negative electrode, the induced electric field atplace at the positive
electrode.
the electrodeThe intense
attracts electric
cations andfield holds
repels ions from
anions, where thetheelectrolyte
opposite andactionelectrons fromatthe
takes place theelectrode.
positive
This is called
electrode. Theasintense
development
electricoffield
charge double-layer,
holds ions from where it stores the
the electrolyte andenergy as potential
electrons from theenergy
electrode.[62].
The shape of CV in Figure 10 depicts rapid switching of ions at the electrode
This is called as development of charge double-layer, where it stores the energy as potential energyelectrolyte interfaces as
well the
[62]. Thegood
shapecapacitive
of CV behavior
in Figureof10 electrodes. The internal
depicts rapid switching resistance
of ionsandatelectrode porosity
the electrode resulted
electrolyte
in current dependence of voltage and makes the shape of the CV plot a less perfect
interfaces as well the good capacitive behavior of electrodes. The internal resistance and electrode rectangular [63].
porosity resulted in current dependence of voltage and makes the shape of the CV plot a less perfect
rectangular [63].
Int.
Int. J.J. Mol.
Mol. Sci. 2019, 20,
Sci. 2019, 20, 3369
x 16 of
16 of 26
26

2.6

2.2

1.8
Current density (mA/cm )
2

1.4

0.6

0.2

-0.2

-0.6

-1

-1.4
0 0.2 0.4 0.6 0.8 1
Potential (V)

Figure 10. CV plot of the fabricated EDLC in the potential range of 0 V to 1 V.

Figure 10.CV plot of the fabricated EDLC in the potential range of 0 V to 1 V.
The charge–discharge profiles of the fabricated EDLC are investigated through galvanostatic
The charge–discharge
technique. Figure 11 shows theprofiles of the fabricated
charge-discharge plot EDLC are investigated
of the fabricated EDLC at through galvanostatic
0.5 mA·cm −2 in the
technique. Figure 11 shows the charge-discharge plot of the fabricated EDLC at
potential range of 0 to 1 V. The discharge slope is observed to be almost linear, which verifies0.5 mA·cm −2 in the
the
potential range
capacitive of 0into
behavior the1 EDLC
V. The[64].
discharge
As the slope is observed
slope of to be
the discharge almost
curve (s) islinear, which the
determined, verifies the
specific
capacitive behavior in the EDLC [64]. As the slope of the discharge curve (s) is determined, the
capacitance (Cs ) can be calculated from the following equation:
specific capacitance (Cs) can be calculated from the following equation:
i
CS = i (8)
C S = sm (8)
sm
here, i is the constant current and m stands for active material mass, which is the mass of active carbon
here,
in this istudy.
is theInconstant
Figure 12, current andEDLC
Cs of the m stands
for 100forcycles
active
canmaterial
be seen,mass, which
in which is the
Cs of theEDLC
mass at
ofthe
active
1st
carbon in this study. In Figure
−1 12, C s of the EDLC for 100 cycles can −1 be seen, in
cycle is found to be 8.7 F·g . Teoh et al. [65] have recorded a Cs of 7.1 F·g for free plasticizer LiClO4which C s of the

EDLCcorn
based at the 1st cycle
starch polymeris found to be EDLC
electrolyte 8.7 F·gtype
−1. Teoh et al. [65] have recorded a Csof 7.1 F·g−1 for
capacitor. At 5th cycle, the Cs drops to 6.5 F·g−1 and free
plasticizer LiClO 4 based corn starch polymer −1 electrolyte EDLC type capacitor. At
remains constant in the range of 6.0 to 6.5 F·g . This capacitance synthesized in the present work is of 5th cycle, the Cs
drops to 6.5 F·g −1 and remains constant in the range of 6.0 to 6.5 F·g−1. This capacitance
the great interest compared to the specific capacitance values of 2.6–3.0 and 1.7–2.1 F·g , which have −1 synthesized
in the
been presentfor
recorded workthe is
EDLCof the great
cells withinterest
the Mg-compared to the
and Li-based specific
PEO capacitance
polymer values
electrolytes of 2.6–3.0
incorporated
and 1.7–2.1F·g −1, which have been recorded for the EDLC cells with the Mg- and Li-based PEO
with ionic liquids [66]. Therefore, polymer blend electrolytes can be established as new materials in
polymer electrolytes
fabricating EDLC cellsincorporated with ionic
with high specific liquids [66]. Therefore, polymer blend electrolytes can
capacitances.
be established as new materials in fabricating EDLC cells with high specific capacitances.
 Int. J. Mol. Sci. 2019, 20, x 17 of 26
Int. J. Mol. Sci. 2019, 20, 3369 17 of 26
Int. J. Mol. Sci. 2019, 20, x 17 of 26
1.2

1.2
1 V drop
1 V drop
0.8
(V) (V)

0.8
Potential

0.6
Potential

0.6
0.4

0.4
0.2

0.2
0
0 20 40 60 80 100 120 140 160 180
0 Time (s)
0 20 40 60 80 100 120 140 160 180
Time (s)
Figure 11.Charge-discharge profiles for the fabricated EDLC at 0.5 mA·cm−2.

Figure 11. Charge-discharge profiles for the fabricated EDLC at 0.5 mA·cm−2.
Figure 11.Charge-discharge profiles for the fabricated EDLC at 0.5 mA·cm−2.
10

109
98
(F/g) (F/g)

87
capacitance

76
capacitance

65
54
Specific

43
Specific

32
21

10
0 20 40 60 80 100 120
0
0 20 40 Cycle60Number 80 100 120

Figure 12. Specific capacitanceCycle

of the Number
fabricated EDLC for 100 cycles.
Figure 12.Specific capacitance of the fabricated EDLC for 100 cycles.
Coulombic efficiency (η) is another
Figure 12.Specific imperative
capacitance parameterEDLC
of the fabricated regarding
for 100the cycling stability of the
cycles.
Coulombic efficiency (η) is another imperative parameter regarding the cycling stability of the
EDLC where it can be calculated from the following equation:
EDLC where it can be calculated from the following equation:
Coulombic efficiency (η) is another imperative parameter regarding the cycling stability of the
t
η = tdd ×equation:
EDLC where it can be calculated from the following 100 (9)
η = tc × 100 (9)
ttc
where discharge and charge time are denoted η =as dtd ×and100tc , respectively. Figure 13 shows the η of(9) the
whereof
EDLC discharge andThe
100 cycles. charge time are
coulombic denotedηas
efficiency, t c tthe
at dand
1sttc,cycle
respectively.
is found Figure 13 shows
to be 20.6% the η of the
and increases to
EDLCand
72.2% of 100 cycles.
86.6% The
at 5th andcoulombic efficiency,
10th cycles, η at the
respectively. At 1st
20th cycle
cycle, η is observed
is found to be 20.6%
to be and increases
92.8% and thento
where discharge and charge time are denoted as tdand tc, respectively. Figure 13 shows the η of the
72.2% and
lowered and86.6% at 5thconstant
remained and 10thatcycles,
92.0% uprespectively.
to 100 cycles.At 20th cycle, η is observed
It is considered to be 92.8%
that the EDLC and
possesses
EDLC of 100 cycles. The coulombic efficiency, η at the 1st cycle is found to be 20.6% and increases to
then lowered
plausible and remained contact
electrode-electrolyte constantasat η is beyond
the92.0% up to 90.0%
100 cycles.
[67]. It is considered that the EDLC
72.2% and 86.6% at 5th and 10th cycles, respectively. At 20th cycle, η is observed to be 92.8% and
possesses plausible electrode-electrolyte contact as the η is beyond 90.0% [67].
then lowered and remained constant at 92.0% up to 100 cycles. It is considered that the EDLC
possesses plausible electrode-electrolyte contact as the η is beyond 90.0% [67].
Int. J. Mol. Sci. 2019, 20, x 18 of 26

Int. J. Mol. Sci. 2019, 20, 3369 18 of 26

Int. J. Mol. Sci. 2019, 20, x 18 of 26
100

80
100
(%)

60
Efficiency

80
(%)

40
60
Efficiency

20
40

0
20
0 20 40 60 80 100 120
Cycle Number
0
0 20
Figure 40stability of the
13.Cycling 60EDLC up to 100
80 cycles. 100 120
Cycle Number
As observed in Figure Figure 11,13.there
Cyclingare stability
tiny potential drops
of the EDLC up (V ) before
to d100 cycles.the discharging process
Figure 13.Cycling stability of the EDLC up to 100 cycles.
commences. This can be related to the existence of internal resistance in the EDLC, which is called
As observed
equivalent in Figure(R11,
series resistance esr).there are tiny potential
This resistance Resrof thedrops
EDLC(V cand ) be
before the discharging
obtained process
from the following
As observed in Figure 11, there are tiny potential drops (Vd) before the discharging process
commences. This can be related to the existence of internal resistance in the EDLC, which is called
equation:
commences. This can be related to the existence of internal resistance in the EDLC, which is called
equivalent series resistance (Resr ). This resistance Resr of the EDLC can be obtained from the following
equivalent series resistance (Resr). This resistance Resrof V the EDLC can be obtained from the following
equation:
equation: Resr = d (10)
Resr = i d
V
(10)
Vid
Figure
Figure 1414shows
showsthe theRResresrofofthetheEDLC
EDLC Resr
forfor
100
100 =cycles.
cycles. It isItdetermined
is determined thatthat
the the
Resr R
varies fromfrom
esr varies (10)
150
to i
150180 Ω over
to 180 the the
Ω over 100100 cycles.
cycles. TheThe existence
existence of of
internal
internal resistance
resistance hashasbeen
beenassumed
assumedtotobe bedue
due to to
various
various factors.
factors. The
The first
first one
one isis from
from the
the electrolyte,
electrolyte, where
where fast fast charge/discharge
charge/discharge process
process causecause
free free
ions
Figure 14 shows the Resr of the EDLC for 100 cycles. It is determined that the Resr varies from 150
ions to recombine and
to recombine reduce the ionic conductivity. Secondly,it is it is from current collectors, which in
to 180 Ω overand thereduce the ionic
100 cycles. The conductivity. Secondly,
existence of internal resistancefrom current
has beencollectors,
assumed which in this
to be due to
this case
case is theis the aluminum
aluminum foil.
foil.one
Lastly, Lastly, it
it is the is the gap
the electrolyte,
gap between between the electrolyte
the electrolyte and electrode,
and electrode, where
wherecause ions
ions from
various factors. The first is from where fast charge/discharge process free
from the electrolyte
the electrolyte andand and electrons
electrons from the carbon electrode form adoublechargelayer
double layer or called
ions to recombine reducefrom the
the ionic carbon electrode
conductivity. form a charge
Secondly, it is from current or called
collectors, potential
which in
potential
energy energy [68].
this case[68].
is the aluminum foil. Lastly, it is the gap between the electrolyte and electrode, where ions
from the electrolyte and electrons from the carbon electrode form a charge double layer or called
potential300 energy [68].

250
300

200
250
ESR (Ohm)

150
200
ESR (Ohm)

100
150

50
100

0
50
0 20 40 60 80 100 120
0 Cycle Number
0 20 40 60 80 100 120
Figure 14. The pattern of equivalent series resistance of the EDLC for 100 cycles.
Figure 14.The pattern of equivalent series resistance of the EDLC for 100 cycles.
Cycle Number

Figure 14.The pattern of equivalent series resistance of the EDLC for 100 cycles.
Int. J. Mol. Sci. 2019, 20, x 19 of 26

The energy density (Ed) and power density (Pd) of the EDLC can be expressed as:
Int. J. Mol. Sci. 2019, 20, 3369 19 of 26
C sV
Ed =
The energy density (Ed ) and power density (Pd ) 2
of the EDLC can be expressed as: (11)

Cs V
Ed = (11)
22
V
Pd = V2 (12)
Pd = 4mResr (12)
4mResr
whereV is the applied voltage (1 V). In
where V is the applied voltage (1 V). In Figure 15, Figure 15, Ed Eis found to be 1.21 Wh·kg−1 at−1the at 1st
thecycle and
d is found to be 1.21 Wh·kg 1st cycle
then lowered to 0.90 Wh·kg −1 at 5th cycle. Edis then kept stable at 0.86 Wh·kg−1 up to 100 cycles. The
and then lowered to 0.90 Wh·kg−1 at 5th cycle. Ed is then kept stable at 0.86 Wh·kg−1 up to 100
E d values of the EDLC are almost constant, which harmonized with the pattern of Cs. The
cycles. The Ed values of the EDLC are almost constant, which harmonized with the pattern of Cs .
stabilization
The stabilization study showed
study showed thatthat
thetheions experience
ions experience thethe
same
sameenergy
energybarrier
barrierduring
duringthe the migration
migration
towards the electrodes from 10th to 100th cycle of charge-discharge process
towards the electrodes from 10th to 100th cycle of charge-discharge process [69]. The energy density [69]. The energy
density achieved for the EDLC cell (0.86 Wh/Kg) in the present work is
achieved for the EDLC cell (0.86 Wh/Kg) in the present work is of great interest compared to that of great interest compared
to that reported
reported (0.3 Wh/Kg)(0.3 Wh/Kg)
for ionic for ionic
liquid liquid incorporated
incorporated PEO basedPEO basedelectrolyte
polymer polymer [66].electrolyte[66].
Figure 16
Figure 16 exhibits the P
exhibits the Pd of the EDLC for 100 cycles. The value of Pd of the EDLC is found to be 643 W·kg 643
d of the EDLC for 100 cycles. The value of Pd of the EDLC is found to be−1
at
W·kg
the 1st at
−1 theand
cycle 1st cycle
droppedandto dropped
571 W·kg to−1
571
at W·kg
−1 at 10th cycle. The interesting observation is that
10th cycle. The interesting observation is that the value
the
of Pvalue of Pd increases back to−1685 W·kg −1 up to 80cycles. In Figure 14, Resrof the EDLC is also
In Figure 14, Resr of the EDLC is also increased at
d increases back to 685 W·kg up to 80cycles.
increased
10th cycle and at 10th cycle until
decreased and decreased
80th cycle. until
At 90th80th
andcycle.
100th At 90ththeand
cycles, EDLC 100th cycles, the
experiences EDLC
reduction
experiences reduction in Pdvalue. This could be related to the growth of ion aggregates/pairs and
in Pd value. This could be related to the growth of ion aggregates/pairs and electrolyte depletion
electrolyte
during rapid depletion during rapid
charge-discharge process.charge-discharge
The main drawbacks process. The main
of polymer drawbacks
electrolyte of polymer
membranes are
electrolyte membranes are ion aggregates/pairs. In this case little ions
ion aggregates/pairs. In this case little ions diffuse to the electrode/electrolyte interface. Consequently, diffuse to the
electrode/electrolyte
the accumulated ion in interface.
the formingConsequently,
double-layer, theataccumulated
the surface ofion thein the forming
electrodes, double-layer,
is reduced, at
and thus,
the surface
reducing theofpower
the electrodes, is reduced, and thus, reducing the power density [61].
density [61].

1.5
E n erg y d en sity W h /K g

0.5

0
0 20 40 60 80 100 120
Cycle Number
Figure 15. Energy density of the fabricated EDLC for 100 cycles.
Figure 15.Energy density of the fabricated EDLC for 100 cycles.
Int.
Int. J.J. Mol.
Mol. Sci.
Sci.2019,
2019,20,
20,x3369 2020of
of 26
26

1000
900
800
P ow er density (W /K g)

700
600
500
400
300
200
100
0
0 20 40 60 80 100 120

Cycle Number
Figure 16. Power density of the fabricated EDLC for 100 cycles.
Figure 16.Power density of the fabricated EDLC for 100 cycles.
3. Experimental Method
3. Experimental Method
3.1. Materials and Sample Preparation
3.1. Materials and Sample Preparation
High molecular weight chitosan (CS) (average molecular weight 310,000–375,000) and Dextran
powderHigh(average
molecular molecular weight(CS)
weight chitosan 35,000–45,000) materials
(average molecular were310,000–375,000)
weight used as the raw andmaterials
Dextran
(Sigma-Aldrich,
powder (average Warrington,
molecularPA, USA). For
weight the fabrication
35,000–45,000) of the polymer
materials were blending
used as based on CS:Dextran,
the raw materials
60 wt.% chitosanWarrington,
(Sigma-Aldrich, and 40 wt.% PA, dextran
USA).wasFordissolved separately
the fabrication of inthe
50 polymer
mL of 1%blending
acetic acid at room
based on
temperature60
CS:Dextran, forwt.%
90 min. Subsequently,
chitosan and 40 wt.% these solutions
dextran then mixed
was dissolved and stirred
separately in 50for
mL3 of h 1%
to gain
acetica
homogeneous
acid blending solution.
at room temperature For Subsequently,
for 90 min. the blended solution of CS:Dextran,
these solutions various
then mixed andamounts
stirred offorLiClO
3 h to4
ranging
gain from 10 to 40blending
a homogeneous wt.% of solution.
LiClO4 inForsteps
theof 10 wassolution
blended added separately with various
of CS:Dextran, continuous stirring
amounts of
to prepare
LiClO CS:Dextran:
4 ranging from 10 to LiTf
40 electrolytes.
wt.% of LiClO The
4 inpolymer
steps of blend
10 waselectrolytes were coded
added separately with as CSDPB1,
continuous
CSDPB2,toCSDPB3,
stirring prepare and CSDPB4LiTf
CS:Dextran: for CS:Dextran
electrolytes.and Theincorporated
polymer blend withelectrolytes
10, 20, 30, and
were40coded
wt.% as of
LiClO4 , respectively.
CSDPB1, CSDPB2, CSDPB3,After casting in different
and CSDPB4 Petri dishes,
for CS:Dextran andthe solutions were
incorporated withleft
10,to
20,dry
30,atand
room
40
temperature
wt.% of LiClO for films to form.After
4, respectively. The films were
casting transferred
in different into
Petri a desiccator
dishes, for further
the solutions weredrying, which
left to dry at
produces
room solvent-free
temperature for films. The
films to thickness
form. of the
The films SPBEM
were was from
transferred into0.0123 to 0.0131for
a desiccator cm.further drying,
which produces solvent-free films. The thickness of the SPBEM was from 0.0123 to 0.0131 cm.
3.2. TNM and LSV Measurements
3.2. TNM
V&Aand LSV Measurements
Instrument DP3003 digital DC power supply was employed to conduct the transference
number
V&A (TNM) analysis
Instrument via DCdigital
DP3003 polarization
DC powermethod [70]. was
supply The cell was polarized
employed at 30the
to conduct mVtransference
and the DC
number (TNM) analysis via DC polarization method [70]. The cell was polarized at 30 mVwas
current was monitored continuously as a function of time at room temperature. Stainless steel andusedthe
as electrodes for TNM due to its ion-blocking characteristic. Ionic and electronic transference
DC current was monitored continuously as a function of time at room temperature. Stainless steel numbers
analyses
was usedareasused to observe
electrodes fortheTNMcontribution
due to its of ion and electron
ion-blocking to the total conductivity
characteristic. Ionic and and prove
electronic
ionic conduction. The potential stability of the highest conducting electrolyte (CSDPB4)
transference numbers analyses are used to observe the contribution of ion and electron to the total was studied
using linear sweep
conductivity voltammetry
and prove (LSV) (DY2300
ionic conduction. Potentiostat)
The potential at sweep
stability rate of 50
of the highest mV·s−1 . For
conducting the LSV
electrolyte
analysis, stainless
(CSDPB4) steel using
was studied was also used
linear as counter,
sweep working
voltammetry and reference
(LSV) electrodes. For
(DY2300 Potentiostat) at both
sweep LSV
rateand
of
50 mV·s . For the LSV analysis, stainless steel was also used as counter, working and referencea
TNM, the
−1 highest conducting electrolyte (CSDPB4) was placed in between two stainless steels in
Teflon conductivity
electrodes. For bothholder,
LSV andas shown
TNM,inthe Figure 17. conducting electrolyte (CSDPB4) was placed in
highest
between two stainless steels in a Teflon conductivity holder, as shown in Figure 17.
Int. J. Mol. Sci. 2019, 20, x 21 of 26
Int. J. Mol. Sci. 2019, 20, 3369 21 of 26
Int. J. Mol. Sci. 2019, 20, x 21 of 26

Figure 17. Schematic diagram of cell arrangement for LSV, TNM and impedance study.
Figure 17. Schematic diagram of cell arrangement for LSV, TNM and impedance study.
Figure 17. Schematic diagram of cell arrangement for LSV, TNM and impedance study.
3.3. EDLC Preparation
3.3. EDLC Preparation
3.3. AnEDLC Preparation
amount of 0.50 g polyvinylidene fluoride (PVdF) was dissolved with stirring in 15
An amount of 0.50 g polyvinylidene fluoride (PVdF) was dissolved with stirring in 15 mL N-methyl
mLN-methylAn amountpyrrolidone
of On (NMP).
0.50theg other On the other hand,
polyvinylidene fluorideactivated
(PVdF) carbon
was (3.25 g) andwith carbon black (0.25
pyrrolidone (NMP). hand, activated carbon (3.25 g) anddissolved
carbon black (0.25 stirring in 15
g) powders
g)mLN-methyl
powders were dry mixed.
pyrrolidone The
(NMP). dryOnmixing
the process
other hand, was carried
activated out
carbon by using
(3.25 g)a planetary
and carbon ball miller
black (0.25
were dry mixed. The dry mixing process was carried out by using a planetary ball miller (XQM-0.4).
(XQM-0.4).
g) powders Six metal
were dry balls were
mixed. Theinserted
dry in theprocess
mixing chamber along
was without
carried thebypowders.
using a The powders
planetary ball were
miller
Six metal balls were inserted in the chamber along with the powders. The powders were mixed at
mixed at rotational
(XQM-0.4). Six metal speed
ballsofwere
500 inserted
r/min forin15 themin. The powders
chamber were then added to powdersthe obtained
rotational speed of 500 r/min for 15 min. The powdersalong werewiththenthe powders.
added to theThe obtained solutionwere
solution
mixed of
at PVdF/NMP
rotational and
speed ofstirred
500 for
r/min 90formin.
15 The
min. homogeneous
The powders solution
were then was
added doctor
to bladed
the on
obtained
of PVdF/NMP and stirred for 90 min. The homogeneous solution was doctor bladed on aluminum
aluminum
solution foil
of and heated
PVdF/NMP at 60stirred
°C for for
a period of time. The electrodes solution
were then stored in desiccator
foil and heated at 60 ◦ Candfor a period of90 min.
time. Theelectrodes
The homogeneous were then stored was indoctor bladed
desiccator on
filled
filled with
aluminum silica gel. The thickness of the electrode was 0.01 cm. The highest conducting electrolyte
with silica foilgel.and
Theheated
thicknessat 60of°C forelectrode
the a period was of time.
0.01Thecm.electrodes
The highest were then stored
conducting in desiccator
electrolyte was
was
filledsandwiched
with silicabetween
gel. The two carbon
thickness of electrodes,
the electrodewhich
was were
0.01 cut into
cm. The circle
highest shape with area
conducting of 2.01 2
electrolyte
sandwiched between two carbon electrodes, which were cut into circle shape with area of 2.01 cm
cmwas
2 and packed in CR2032 coin cells. The schematic diagram of the EDLC cell is shown in Figure 18.
and sandwiched
packed in CR2032between cointwo carbon
cells. Theelectrodes,
schematicwhich diagram wereof cut
theinto
EDLC circle
cellshape
is shown withinarea of 2.01
Figure 18.
The
cm 2galvanostatic
and packed incharge-discharge
CR2032 coin characteristics
cells. The schematic ofdiagram
the EDLC of were
the EDLC carried
cell out
is usinginaFigure
shown battery 18.
The galvanostatic charge-discharge characteristics of the EDLC were carried out using a battery cycler
cycler
The (Neware, Shenzhen,
galvanostatic China) with a current density of
−2 . 0.5 mA·cm −2. Digi-IVY DY2300
(Neware, Shenzhen,charge-discharge
China) with a current characteristics
density of of 0.5the EDLC
mA·cm were carried
Digi-IVY DY2300 out Potentiostat
using a battery was
Potentiostat
cycler was
(Neware, used to conduct
Shenzhen, cyclic
China) voltammetry
with a current (CV) of
densitythe EDLC
of−1 0.5 at 10
mA·cm mV·s−2 .
−1 in the potential
Digi-IVY DY2300
used to conduct cyclic voltammetry (CV) of the EDLC at 10 mV·s in the potential window of 0–1 V.
window of 0–1was
Potentiostat V. used to conduct cyclic voltammetry (CV) of the EDLC at 10 mV·s−1 in the potential
window of 0–1 V.

Figure
Figure 18.18. Diagram
Diagram ofof
thethe EDLC
EDLC cell
cell forfor
CVCV and
and galvanostatic
galvanostatic charge-dischargemeasurement.
charge-discharge measurement.

Figure 18.
3.4. Structural, Diagram of the
Morphological, andEDLC cell for Characterizations
Impedance CV and galvanostatic charge-discharge measurement.
3.4. Structural, Morphological, and Impedance Characterizations
Spotlight Morphological,
3.4. Spotlight
Structural, 400 Perkin-Elmer spectrometer
andspectrometer
Impedance was used in conducting Fourier transform infrared
Characterizations
400 Perkin-Elmer was used in conducting Fourier transform infrared
(FTIR) spectroscopy with a resolution of 1 cm−1−1 (450–4000 cm −1 ). The surface of the electrolyte was
(FTIR)Spotlight
spectroscopy with a resolution
400 Perkin-Elmer of 1
spectrometer cm (450–4000 cm −1). The surface of the electrolyte was
analyzed via Hitachi SU8220 FESEM with 10K×was used in conducting
magnification. Fourier
For structural transform
analysis, XRDinfrared
pattern
analyzed
(FTIR) via Hitachi
spectroscopy SU8220
with a FESEM
resolutionwith
of 10K×
1 cm magnification.
−1 (450–4000 cm For
−1). structural
The surfaceanalysis,
of the XRD pattern
electrolyte was
was acquired via D5000 X-ray diffractometer (1.5406 Å). The 2θ angle was continuously altered from
was acquired
analyzed viavia D5000SU8220
Hitachi X-ray diffractometer
FESEM with (1.5406
10K× Å). The 2θ angle
magnification. For was continuously
structural analysis,altered
XRD from
pattern
5 to 80 (resolution = 0.1 ). In the mechanism study, HIOKI 3532–50 LCR HiTESTER was employed
◦ ◦ ◦
5°was
to 80° (resolution
acquired = 0.1°).
via D5000 In the
X-ray mechanism study,
diffractometer (1.5406HIOKI
Å). The3532–50
2θ angle LCR
wasHiTESTER wasaltered
continuously employed
from
5° to 80° (resolution = 0.1°). In the mechanism study, HIOKI 3532–50 LCR HiTESTER was employed
Int. J. Mol. Sci. 2019, 20, 3369 22 of 26

to analyze electrical impedance spectroscopy (EIS) measurements of the samples (50 Hz to 5 MHz).
The cell arrangement for EIS is shown in Figure 17.

4. Conclusions
Solid polymer blend electrolytes (SPBE) composed of chitosan and dextran incorporated with
various amounts of lithium perchlorate (LiClO4 ) was prepared. The relatively highest ion conducting
sample was utilized to fabricate EDLC supercapacitor. Non-crystalline behavior of the polymer blend
electrolytes has been confirmed from XRD pattern. The FTIR emphasized the strong interaction between
the constituents of polymer electrolyte. The relatively smooth surface morphology of the electrolyte
was found to be an indication of compatible LiClO4 /polymer system. Faradaic process has shown to be
absent and has definitely been noticed in the cyclic voltammetry. The conductivity of the samples was
measured using impedance spectroscopy. The ionic (ti ) and electronic (te ) transference number for
the highest conducting electrolyte were found to be 0.98 and 0.02, respectively. The electrochemical
stability window, as estimated from cyclic voltammetry, was found to be around 2.25 V for the Li+ ion
conducting electrolyte. The absence of a peak in CV plot indicating the presence of electrical double
layer at the surface of the electrodes. The highest ion conducting samples was used to fabricate the
EDLC supercapacitor. The discharge slope has been observed to be almost linear, which verified that
the EDLC possesses the capacitive behavior. The performance of fabricated EDLC was also studied
using cyclic voltammetry and charge–discharge techniques. The highest specific capacitance was
achieved to be at 8.7 F·g−1 . At 20th cycle, the efficiency (η) was observed at 92.8%, where it remained
constant at 92.0% up to 100 cycles. It was found that the EDLC possesses good electrode-electrolyte
contact as η is above 90.0%. Another key finding is that the Resr was quite low and varied from 150 to
180 Ω over the 100 cycles. The energy density was quite high and equal to 1.21 Wh·kg−1 at the 1st
cycle and then kept stable at 0.86 Wh·kg−1 up to 100 cycles. Lastly, the value of Pd was also found to
increase, returning to 685 W·kg−1 up to 80 cycles.

Author Contributions: Conceptualization, Supervision, Methodology, Project Administration, Investigation,

Writing—Original Draft Preparation, S.B.A.; Methodology, Investigation, Writing—Original Draft Preparation,
Formal Analysis, M.H.H.; Writing—Review & Editing, Conceptualization, M.F.Z.K.; Writing—Review & Editing,
Validation, W.O.K.; Writing—Review & Editing R.M.A.
Funding: This research was funded by Ministry of Higher Education and Scientific Research-Kurdish National
Research Council (KNRC), Kurdistan Regional Government/Iraq. The financial support from the University of
Sulaimani and Komar Research Center (KRC), Komar University of Science and Technology is greatly appreciated.
Acknowledgments: The authors gratefully acknowledge the Ministry of Higher Education and the Scientific
Research, Kurdistan Regional Government/Iraq, University of Sulaimani, University of Malaya and Komar
Research Center (KRC), Komar University of Science and Technology for supporting this research project.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Iro, Z.S.; Subramani, C.; Dash, S.S. A Brief Review on Electrode Materials for Supercapacitor. Int. J.
Electrochem. Sci. 2016, 11, 10628–10643. [CrossRef]
2. Kiamahalleh, M.V.; Zein, S.S.H.; Najafpour, G.; Sata, S.A.; Buniran, S. Multiwalled carbon nanotubes based
nanocomposites for supercapacitors: A review of electrode materials. Nano 2012, 7, 1230002. [CrossRef]
3. Shobana, V.; Parthiban, P.; Balakrishnan, K. Lithium based battery-type cathode material for hybrid
supercapacitor. J. Chem. Pharm. Res. 2015, 7, 207–212.
4. Kamarudin, K.H.; Hassan, M.; Isa, M.I.N. Lightweight and Flexible Solid-State EDLC based on Optimized
CMC-NH4NO3 Solid Bio-Polymer Electrolyte. ASM Sci. J. Spec. Issue 2018, 1, 29–36.
5. Shukur, A.; Fadhlullah, M. Characterization of Ion Conducting Solid Biopolymer Electrolytes Based on
Starch-Chitosan Blend and Application in Electrochemical Devices. Ph.D. Dissertation, University of Malaya,
Wilayah Persekutuan Kuala Lumpur, Malaysia, 2015.
Int. J. Mol. Sci. 2019, 20, 3369 23 of 26

6. Kadir, M.F.Z.; Salleh, N.S.; Hamsan, M.H.; Aspanut, Z.; Majid, N.A.; Shukur, M.F. Biopolymeric electrolyte
based on glycerolized methyl cellulose with NH4Br as proton source and potential application in EDLC.
Ionics 2017, 24, 1651–1662. [CrossRef]
7. 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. accpected for publication.
8. 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]
9. Hamsan, M.H.; Aziz, B.; Shukur, M.F.; Kadir, M.F.Z. Protonic cell performance employing electrolytes based
on plasticized methylcellulose-potato starch-NH4NO3. Ionics 2019, 25, 559–572. [CrossRef]
10. Nyuk, C.M.; Isa, M.I.N. Solid biopolymer electrolytes based on carboxymethyl cellulose for use in coin cell
proton batteries. J. Sustain. Sci. Manag. 2018, 2017, 42–48.
11. Salleh, N.S.; Aziz, S.B.; Aspanut, Z.; Kadir, M.F.Z. Electrical impedance and conduction mechanism analysis of
biopolymer electrolytes based on methyl cellulose doped with ammonium iodide. Ionics 2016, 22, 2157–2167.
[CrossRef]
12. Hassan, M.F.; Azimi, N.S.N.; Kamarudin, K.H.; Sheng, C.K. Solid Polymer Electrolytes Based on
Starch-Magnesium Sulphate: Study on Morphology and Electrical Conductivity. ASM Sci. J. Spec. Issue 2018,
1, 17–28.
13. Du, B.W.; Hu, S.Y.; Singh, R.; Tsai, T.T.; Lin, C.C.; Ko, F.U. Eco-Friendly and Biodegradable Biopolymer
Chitosan/Y2 O3 Composite Materials in Flexible Organic Thin-Film Transistors. Materials 2017, 10, 1026.
14. Moniha, V.; Alagar, M.; Selvasekarapandian, S.; Sundaresan, B.; Hemalatha, R.; Boopathi, G. Synthesis and
characterization of bio-polymer electrolyte based on iota-carrageenan with ammonium thiocyanate and its
applications. J. Solid State Electrochem. 2018, 22, 3209–3223. [CrossRef]
15. Netsopa, S.; Niamsanit, S.; Sakloetsakun, D.; Milintawisamai, N. Characterization and Rheological Behavior
of Dextran from Weissella confusa R003. Int. J. Polym. Sci. 2018, 2018, 5790526. [CrossRef]
16. 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.
17. Barsbay, M.; Guner, A. Miscibility of dextran and poly(ethylene glycol) in solid state: Effect of the solvent
choice, Carbohydr. Polymers 2007, 69, 214–223. [CrossRef]
18. Telegeev, G.; Kutsevo, N.; Chumachenko, V.; Naumenko, A.; Telegeeva, P.; Filipchenko, S.; Harahuts, Y.
Dextran-Polyacrylamide as Matrices for Creation of Anticancer Nanocomposite. Int. J. Polym. Sci. 2017,
2017, 4929857. [CrossRef]
19. Misenan, M.S.M.; Isa, M.I.N.; Khiar, A.S.A. Electrical and structural studies of polymer electrolyte based on
chitosan/methyl cellulose blend doped with BMIMTFSI. Mater. Res. Express 2018, 5, 055304. [CrossRef]
20. Hamsan, M.H.; Shukur, M.F.; Kadir, M.F.Z. The effect of NH4NO3 towards the conductivity enhancement
and electrical behavior in methyl cellulose-starch blend based ionic conductors. Ionics 2017, 23, 1137–1154.
[CrossRef]
21. Kharbachi, A.E.; Hu, Y.; Yoshida, K.; Vajeeston, P.; Kim, S.; Sørby, M.H.; Orimo, S.; Fjellvåg, H.; Hauback, B.C.
Lithium ionic conduction in composites of Li(BH4)0.75I0.25 and amorphous 0.75Li2S0.25P2S5 for battery
applications. Electrochim. Acta 2018, 278, 332–339. [CrossRef]
22. Tamilselvi, P.; Hema, M. Conductivity studies of LiCF3SO3 doped PVA: PVdF blend polymer electrolyte.
Physica B 2014, 437, 53–57. [CrossRef]
23. 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, 035701–035711. [CrossRef]
24. Kadir, M.F.Z.; Hamsan, M.H. 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]
25. Aziz, S.B.; Abidin, Z.H.Z.; Kadir, M.F.Z. Innovative method to avoid the reduction of silver ions to silver
nanoparticles in silver ion conducting based polymer electrolytes. Phys. Scr. 2015, 90, 035808. [CrossRef]
26. Aziz, S.B.; Kadir, M.F.Z.; Abidin, Z.H.Z. Structural, morphological and electrochemical impedance study of
CS:LiTf based solid polymer electrolyte: Reformulated Arrhenius equation for ion transport study. Int. J.
Electrochem. Sci. 2016, 11, 9228–9244. [CrossRef]
Int. J. Mol. Sci. 2019, 20, 3369 24 of 26

27. Hamsan, M.H.; Shukur, M.F.; Aziz, S.B.; Kadir, M.F.Z. Dextran from Leuconostoc mesenteroides-doped
ammonium salt-based green polymer electrolyte. Bull. Mater. Sci. 2019, 42, 57. [CrossRef]
28. Aziz, S.B.; Abidin, Z.H.Z.; Arof, A.K. Effect of silver nanoparticles on the DC conductivity in chitosan–silver
triflate polymer electrolyte. Physica B 2010, 405, 4429–4433. [CrossRef]
29. Malathi, J.; Kumaravadivel, M.; Brahmanandhan, G.M.; Hema, M.; Baskaran, R.; Selvasekarapandian, S.
Structural, thermal and electrical properties of PVA–LiCF3SO3 polymer electrolyte. J. Non-Cryst. Solids 2010,
356, 2277–2281. [CrossRef]
30. Aziz, S.B. Role of dielectric constant on ion transport: Reformulated Arrhenius equation. Adv. Mater. Sci. Eng.
2016, 2016, 2527013. [CrossRef]
31. Shukla, R.; Shukla, S.; Bivolarski, V.; Iliev, I.; Ivanova, I.; Goyal, A. Structural Characterization of Insoluble
Dextran Produced by Leuconostoc mesenteroides NRRL B-1149 in the Presence of Maltose. Food Technol.
Biotechnol. 2011, 49, 291–296.
32. 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]
33. Dumitraşcu, M.; Meltzer, V.; Sima, E.; Vîrgolici, M.; Albu, M.G.; Ficai, A.; Moise, V.; Minea, R.; Vancea, C.;
Scărişoreanu, A.; et al. Characterization of electron beam irradiated collagenpolyvinylpyrrolidone (PVP)
and collagen-dextran (DEX) blends. Dig. J. Nanomater. Biostruct. 2011, 6, 1793–1803.
34. Aziz, S.B.; Abidin, Z.H.Z. Electrical conduction mechanism in solid polymer electrolytes: New concepts to
arrhenius equation. J. Soft Matter 2013, 2013, 323868. [CrossRef]
35. Nikoli, G.S.; Caki, M.; Miti, Z.; Ili, B.; Premovic, P. Attenuated Total Reflectance–Fourier Transform Infrared
Microspectroscopy of Copper(II) Complexes with Reduced Dextran Derivatives. Russian J. Phys. Chem. A
2009, 83, 1520–1525. [CrossRef]
36. Wei, D.; Sun, W.; Qian, W.; Ye, Y.; Ma, X. The synthesis of chitosan-based silver nanoparticles and their
antibacterial activity. Carbohydr. Res. 2009, 344, 2375–2382. [CrossRef] [PubMed]
37. Mitić, Ž.; Cakić, M.; Nikolić, G. Fourier-Transform IR spectroscopic investigations of Cobalt(II)–dextran
complexes by using D2O isotopic exchange. Spectroscopy 2010, 24, 269–275. [CrossRef]
38. Han, C.C.; Shi, W.; Jin, J. Morphology and Crystallization of Crystalline/Amorphous Polymer Blends.
Encyclopedia Polym. Compos. 2013, 1–19. [CrossRef]
39. 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]
40. Aziz, S.B.; Abdullah, O.G.; Rasheed, M.A.; Ahmed, H.M. Effect of high salt concentration (HSC) on structural,
morphological, and electrical characteristics of chitosan based solid polymer electrolytes. Polymers 2017, 9,
187. [CrossRef]
41. Shukur, M.F.; Kadir, M.F.Z. Hydrogen ion conducting starch-chitosan blend based electrolyte for application
in electrochemical devices. Electrochim. Acta 2015, 158, 152–165. [CrossRef]
42. Polu, A.R.; Kumar, R. AC impedance and dielectric spectroscopic studies of Mg2+ionconducting PVA–PEG
blended polymer electrolytes. Bull. Mater. Sci. 2011, 34, 1063–1067. [CrossRef]
43. Aziz, S.B.; Woo, T.J.; Kadir, M.F.Z.; Ahmed, H.M. A conceptual review on polymer electrolytes and ion
transport models. J. Sci. Adv. Mater. Devices 2018, 3, 1–17. [CrossRef]
44. Aziz, S.B.; Abidin, Z.H.Z.; Arof, A.K. Influence of silver ion reduction on electrical modulus parameters of
solid polymer electrolyte based on chitosan-silver triflate electrolyte membrane. ExpressPolym. Lett. 2010, 4,
300–310. [CrossRef]
45. Aziz, S.B. The mixed contribution of ionic and electronic carriers to conductivity in chitosan based solid
electrolytes mediated by CuNt Salt. J. Inorg. Organomet. Polym. 2018, 28, 1942. [CrossRef]
46. Hirankumar, G.; Selvasekarapandian, S.; Bhuvaneswari, M.S.; Baskaran, R.; Vijayakumar, M. AC Impedance
Studies on Proton Conducting Polymer Electrolyte Complexes (PVA+CH3COONH 4). Ionics 2004, 10, 135.
[CrossRef]
47. Aziz, S.B.; Faraj, M.G.; Abdullah, O.G. Impedance Spectroscopy as a Novel Approach to Probe the Phase
Transition and Microstructures Existing in CS:PEO Based Blend Electrolytes. Sci. Rep. 2018, 8, 14308.
[CrossRef] [PubMed]
48. Eftekhari, A. The mechanism of ultrafast supercapacitors. J. Mater. Chem. A. 2018, 6, 2866–2876. [CrossRef]
Int. J. Mol. Sci. 2019, 20, 3369 25 of 26

49. Eftekhari, A. Surface Diffusion and Adsorption in Supercapacitors. ACS Sustain. Chem. Eng. 2019, 7,
3692–3701. [CrossRef]
50. Pradhan, D.K.; Choudhary, P.; Samantaray, B.K.; Karan, N.K.; Katiyar, R.S. Effect of Plasticizer on Structural
and Electrical Properties of Polymer Nanocompsoite Electrolytes. Int. J. Electrochem. Sci. 2007, 2, 861–871.
51. Mohapatra, S.R.; Thakur, A.K.; Choudhary, R.N.P. Effect of nanoscopic confinement on improvement in ion
conduction and stability properties of an intercalated polymer nanocomposite electrolyte for energy storage
applications. J. Power Sources 2009, 191, 601–613. [CrossRef]
52. 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]
53. Aziz, S.; 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]
54. Teo, L.P.; Buraidah, M.H.; Nor, A.F.M.; Majid, S.R. Conductivity and dielectric studies of Li2SnO3. Ionics
(Kiel) 2012, 18, 655–665. [CrossRef]
55. Hema, M.; Selvasekarapandian, S.; Arunkumar, D.; Sakunthala, A.; Nithya, H.F.T.I.R. FTIR, XRD and
ac impedance spectroscopic study on PVA based polymer electrolyte doped with NH4X (X = Cl, Br, I).
J. Non-Cryst. Solids 2009, 355, 84–90. [CrossRef]
56. Kufian, M.Z.; Aziz, M.F.; Shukur, M.F.; Rahim, A.S.; Ariffin, N.E.; Shuhaimi, N.E.A.; Arof, A.K. PMMA-LiBOB
gel electrolyte for application in lithium ion batteries. Solid State Ionics 2012, 208, 36–42. [CrossRef]
57. Diederichsen, K.M.; McShane, E.J.; McCloskey, B.D. McCloskey Promising Routes to a High Li+ Transference
Number Electrolyte for Lithium Ion Batteries. ACS Energy Lett. 2017, 2, 2563–2575. [CrossRef]
58. Othman, L.; Isa, K.B.; Osman, Z.; Yahya, R. Ionic Conductivity, Morphology and Transport Number of
Lithium Ions in PMMA Based Gel Polymer Electrolytes. Defect Diffus. Forum 2013, 334–335, 137–142.
[CrossRef]
59. Sampathkumar, L.; Selvin, P.C.; 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]
60. Monisha, S.; Mathavan, T.; Selvasekarapandian, S.; Benial, A.M.F.; Premalatha, M. Preparation and
characterization of cellulose acetate and lithium nitrate for advanced electrochemical devices. Ionics
2017, 23, 2697–2706. [CrossRef]
61. Liew, C.W.; Ramesh, S. Electrical, structural, thermal and electrochemical properties of corn starch-based
biopolymer electrolytes. Carbohydr. Polym. 2015, 124, 222–228. [CrossRef]
62. 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, 217–220. [CrossRef]
63. Bandaranayake, C.M.; Weerasinghe, W.A.D.; Vidanapathirana, K.P.; Perera, K.S. A Cyclic Voltammetry study
of a gel polymer electrolyte based redox-capacitor. Sri. Lankan J. Phys. 2015, 16, 19–27. [CrossRef]
64. Teoh, K.H.; Liew, C.W.; Ramesh, S. Electric double layer capacitor based on activated carbon electrode and
biodegradable composite polymer electrolyte. Ionics 2014, 20, 251–258.
65. Teoh, K.H.; Lim, C.S.; Liew, C.W.; Ramesh, S. Electric double-layer capacitors with corn starch-based
biopolymer electrolytes incorporating silica as filler. Ionics 2015, 21, 2061–2068. [CrossRef]
66. Pandey, G.P.; Kumar, Y.; Hashmi, S.A. Ionic liquid incorporated PEO based polymer electrolyte for electrical
double layer capacitors: A comparative study with lithium and magnesium systems. Solid State Ionics 2011,
190, 93–98. [CrossRef]
67. 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]
68. Arof, A.K.; Kufian, M.Z.; Syukur, M.F.; Aziz, M.F.; Abdelrahman, A.E.; Majid, S.R. Electrical double layer
capacitor using poly(methyl methacrylate)–C4BO8Li gel polymer electrolyte and carbonaceous material
from shells of mata kucing (Dimocarpus longan) fruit. Electrochim. Acta 2012, 74, 39–45. [CrossRef]
Int. J. Mol. Sci. 2019, 20, 3369 26 of 26

69. Hamsan, M.H.; Shukur, M.F.; Kadir, M.F.Z. NH4 NO3 as charge carrier contributor in glycerolized potato
starch-methyl cellulose blend-based polymer electrolyte and the application in electrochemical double-layer
capacitor. Ionics 2017, 23, 3429–3453. [CrossRef]
70. 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]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).