Results in Physics 15 (2019) 102584

Contents lists available at ScienceDirect

Results in Physics
journal homepage: www.elsevier.com/locate/rinp

Fabrication of energy storage EDLC device based on CS:PEO polymer blend T

electrolytes with high Li+ ion transference number
⁎
Shujahadeen B. Aziza,b, , M.H. Hamsanc, M.A. Brzad, M.F.Z. Kadirc, Rebar T. Abdulwahide,
Hewa O. Ghareebf, H.J. Woog
a
Advanced Polymeric Materials Research Lab., Department of Physics, College of Science, University of Sulaimani, Qlyasan Street, Sulaimani, Kurdistan Regional
Government, Iraq
b
Komar Research Center (KRC), Komar University of Science and Technology, Kurdistan Regional Government, Sulaimani 46001, Iraq
c
Centre for Foundation Studies in Science, University of Malaya, Kuala Lumpur, Malaysia
d
Faculty of Engineering, International Islamic University of Malaysia, Kuala Lumpur, Gombak, Malaysia
e
Department of Physics, College of Education, University of Sulaimani, Kurdistan Regional Government, Old Campus, Sulaimani, Iraq
f
Department of Chemistry, College of Science, University of Sulaimani, Kurdistan Regional Government, Qlyasan Street, Sulaimani, Iraq
g
Centre for Ionics, Faculty of Science, University of Malaya, Kuala Lumpur, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: High ion transference number polymer blend electrolytes of chitosan (CS):poly (ethylene oxide) (PEO):LiClO4
Polymer blend electrolytes systems were synthesized using solution cast technique. The XRD analysis indicated that the crystalline peaks of
XRD and FTIR study CS vanished in CS:PEO host blend polymer. The intensity of the hump observed in CS:PEO blend film decreased
TNM and LSV analysis upon addition of LiClO4 salt. The FTIR study revealed the complex formation between the CS:PEO and added salt
Cyclic voltammetry
through the shifting and lessening in intensity of the FTIR bands corresponding to the functional groups. The
EDLC
bulk resistance estimated from the impedance plots decreased with increasing salt concentration. The maximum
DC conductivity was found to be 7.34 × 10−4 S cm−1 for CS:PEO incorporated with 40 wt% of LiCLO4 salt. The
electrical equivalent circuit (EEC) model has been carried out for selected samples to clarify the common picture
of the electrical properties of the system. It has been verified via transference number analysis (TNM) that the
transport mechanism in CS:PEO:LiClO4 electrolyte is predominantly ionic in nature with tion = 0.993 and
tel = 0.007. The high ion transference number and high DC conductivity emphasized the possibility of the
samples for electrochemical device application. From linear sweep voltammetry (LSV) investigation,
CS:PEO:LiClO4 electrolyte was found to be electrochemically constant as the voltage sweep linearly up to 2.24 V.
The CV curve covered most of the area of the current–potential plot with no redox peaks. The DC conductivity
value, TNM and LSV results revealed the availability of the samples for electrical double layer capacitor (EDLC)
application. The existence of charges double-layer in the fabricated EDLC was proven from cyclic voltammetry
(CV). EDLC showed a consistent performance of specific capacitance (6.88 F g−1), energy density
(0.94 Wh kg−1) and power density (305 W kg−1) for complete 100 cycles at a current density of 0.5 mA cm−2.

Introduction straightforward processing, cost-effectiveness, and productivity to the

lack of internal shorting and leakage of electrolytes [4,5]. At the same
A series of research initiatives have focused on amorphous polymer time, in comparison with inorganic solids, polymer electrolytes are
salt complexes with respect to the promising role they could play in superior in terms of flexibility [6]. Polymer electrolytes can be prepared
various devices, including fuel cells, batteries, electrochromic displays, by dissolving metal salts in a polymeric matrix and consequently dis-
sensors, and supercapacitors [1–3]. Applications in these areas have sociated into metal cations and corresponding counter anions. These
been identified as viable because the polymer electrolytes are asso- types of polymers are conductive ionically and thereby have received
ciated with numerous advantages in comparison to traditional mate- considerable attention owing to their applications in versatile electro-
rials. As documented in the literature, these advantages range from chemical devices [7]. Natural polymers are also environmentally

⁎
Corresponding author at: Advanced Polymeric Materials Research Lab., Department of Physics, College of Science, University of Sulaimani, Qlyasan Street,
Sulaimani, Kurdistan Regional Government, Iraq.
E-mail addresses: [email protected], [email protected], [email protected] (S.B. Aziz).

https://doi.org/10.1016/j.rinp.2019.102584
Received 12 June 2019; Received in revised form 31 July 2019; Accepted 10 August 2019
Available online 19 August 2019
2211-3797/ © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

friendly solid polymer electrolytes and showed important character- labelled Petri dishes, films were formed by leaving the solutions to dry
istics to be implemented in electrochemical devices such as electro- at room temperature and the resulting films were further dried in a
chromic devices, high energy density batteries, sensors and fuel cells desiccator. In this way, the procedure allowed generating the films
[8]. Solid polymer electrolytes are interesting alternative to liquid containing no solvents, and the fabricated polymers have been utilized
electrolytes in dye-sensitized solar cells [9–13]. Recently, biodegrad- as raw materials.
able nature of natural polymers, for example, starch, cellulose, chit-
osan, carrageenan, and agarose have shown promising characteristics to TNM and LSV measurements
be intensively explored by many researcher groups as those are non-
toxic and easy to use in electrolyte preparation [14]. For example, V & A Instrument DP3003 digital DC power supply was employed to
Chitosan (CS) as deacetylated product is one derivatives of chitin, to- perform the transference number (TNM) analysis via DC polarization
gether with cellulose are one of the most abundant biopolymer in method [38]. The highest conducting electrolyte was sandwiched be-
nature [15]. It is mainly obtained from shrimp waste and considerably tween blocking electrodes (stainless steel) of a Teflon holder. The cell
used as a natural polymer in many potential applications [16]. The best was polarized at 30 mV and the DC current monitored as a function of
available knowledge indicates that as a result of the enrichment in polar time at the ambient temperature. The potential stability of the elec-
groups (NH2 and OH) within the chains and served as conjunction sites, trolyte was explored using linear sweep voltammetry (LSV) analysis
chitosan is a prevalent sorbent with a high affinity for transition metal (DY2300 potentiostat). The relatively high conducting electrolyte was
ions [17]. The capacity that the chitosan has for moulding into a range placed between two stainless steel in Teflon conductivity holder at a
of forms is considered as a vital property, with these forms ranging from scan rate used was 50 mV s−1.
hydrogels and porous scaffolds to films [18]. Several ion-conducting
polymer electrolytes based on chitosan have been documented, in-
EDLC preparation
cluding CS-NH4NO3-EC [19], CS- NH4CF3SO3 [20], CS -LiCF3SO3-EC
[21], CS -NH4I-EC [22], CS -PVA-NH4NO3-EC [23], CS -NaClO4 [24]
A 0.50 g of polyvinylidene fluoride (PVdF) was stirred in 15 mL N-
and CS -AgNO3 [25]. The most obvious properties of chitosan are re-
methyl pyrrolidone (NMP). Activated carbon (3.25 g) and carbon black
latively crystalline in structure, high molecular weight polysaccharide
(0.25 g) powders were mixed using planetary ball miller to gain a
and robust structure as a result of intermolecular or intramolecular
homogeneous solution. The mixture of activated carbon and carbon
hydrogen bonds [26,27]. The applicability of chitosan depends on in-
black was poured in the PVdF solution. The homogeneous solution was
creasing both amorphous phase and ionic conductivity in polymers;
doctor bladed on aluminum foil and heated at 60 °C for a certain time.
additionally, blending of polar polymer methodology has been reported
The electrodes were stored in a dessicator filled with silica gel. The
[28,29].
relatively high conducting electrodes was sandwiched between two
In the present work, chitosan is combined with PEO polymer.
carbon electrodes and packed in CR2032 coin cells. The galvanostatic
Several polymers, including polyvinyl pyrrolidone (PVP) [28], boroxine
charge-discharging characteristics of the EDLC were performed using a
ring polymer (BP) [29], polyacrylonitrile (PAN) [30,31], and poly(di-
battery cycler (Neware) with a current density of 0.5 mA cm−2. Digi-
thiooxamide) (PDTOA) [32] have been mixed with PEO based elec-
IVY DY2300 Potentiostat was used to carry out cyclic voltammetry (CV)
trolytes. Based on previous work [33], the optimum ratio is 70 wt%
of the EDLC in the potential window of 0 to 1 V at 10 mV s−1. The
chitosan and 30 wt% PEO where amorphous structure was prevalent.
schematic diagram of the EDLC cell was shown in scheme 1.
Similarly, in the present work, 70 wt% chitosan- 30 wt% PEO is chosen
with various concentration of lithium perchlorate (LiClO4). Thereby, a
relatively highest conducting electrolyte has been obtained as electrode Structural and impedance characterizations
separators in the EDLC. EDLC is considered as an alternative for con-
ventional batteries. The mechanism of energy storage for EDLC involves Spotlight 400 Perkin-Elmer spectrometer was used to conduct
non-Faradaic process where there is no electron exchange and alter- Fourier transform Infrared (FTIR) spectroscopy with a resolution of
natively ions establish double-layer on the carbon-based electrodes 1 cm−1 (450–4000 cm−1). The XRD analysis was performed via D5000
X-ray diffractometer (1.5406 Å). The 2θ angle was varied from 5° to 80°
[34]. Advantages involving EDLC are relatively higher power density,
(Resolution = 0.1°). The HIOKI 3532–50 LCR HiTESTER, which hy-
durable, better thermal stability, higher reversibility, cheaper, safer and
phenates to a computer in the 42 Hz to 5,000 kHz frequency range, was
simpler fabrication methods when compared to Faradaic capacitor or
employed to measure the films’ impedance at the room temperature.
pseudocapacitor [35-37]. Therefore, the main aim of the current work
The usage of the software is to control the measurements as well as the
is to investigate the suitability of CS:PEO based polymer electrolyte for
calculation of both the imaginary and real parts of the impedance
EDLC applications.
spectrum. Discs with a diameter of 20 mm were produced from the SPE
Experimental method

Materials and sample preparation

High molecular weight chitosan (CS) (average molecular weight

310,000–375,000) and poly (ethylene oxide) powder (average mole-
cular weight 300,000) materials were supplied by Sigma-Aldrich. For
the preparation of the polymer blend based on chitosan: poly(ethylene
oxide) [CS:PEO], 70 wt% chitosan and 30 wt% poly(ethylene oxide)
were dissolved separately, each in 50 mL of 1% acetic acid at room
temperature for 120 min. Subsequently, the solution mixed and stirred
for 3 h to obtain a homogeneous blending solution. For the blended
solution of CS:PEO, different amounts of LiClO4 from 10 to 40 wt% in
steps of 10 were added separately with continuous stirring to obtain CS:
PEO: LiClO4 electrolytes. The polymer blend electrolytes were coded as
CSPB1, CSPB2, CSPB3, and CSPB4 for CS: PEO incorporated with 10,
20, 30, and 40 wt% of LiClO4, respectively. Following casting in the Scheme1. Diagram of the EDLC cell.

2
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

Fig. 1. XRD pattern for (a) pure CS and (b) CS:PEO films.

films and, in turn, these were sandwiched within a pair of stainless steel CS:PEO are almost disappeared and the intensity of the peak moder-
electrodes under spring pressure. For the complex impedance (Z*), the ately decreased. Nevertheless, with the addition of 40 wt% of LiClO4
imaginary (Zi) and real (Zr) parts were employed using the relations (see Fig. 2b), CS: PEO’s hump exhibited broad, and more lesser in the
given below to calculate the dc conductivity (σdc). intensity of the peak. This is due to the elimination of the hydrogen
bonding between amino groups and hydroxyl groups, which is re-
1 t
σdc = ⎛ ⎞ × ⎛ ⎞
⎜ ⎟ sponsible for complexation between lithium perchlorate salt and
⎝ Rb ⎠ ⎝ A ⎠ (1) CS:PEO. Hence, the amorphous phase predominates within the sample,
and a few crystalline peaks with low intensities are exist [43,44]. The
where t is the thickness and A is the area of the film, Rb is the bulk
new peaks can be ascribed to a sort of short-range order, which is es-
resistance of the film derived from the intercept of the impedance plot
tablished as a result of ion multiples existence [45]. It is interesting to
on the real axis.
note, though, Sanders et. al [46] have accounted for the new peaks with
reference to the complex development between polymer and salt as
Results and discussion opposed to pure salt.

XRD study
FTIR analysis
To investigate the structural behavior of the samples, the XRD
patterns were acquired. The XRD patterns of pure CS and CS: PEO films Fourier transform infrared (FTIR) spectroscopy has been widely
are shown in Fig. 1(a,b). Evidence revealed that pure chitosan is used in the study of the formation of polymeric blends. FTIR spectro-
characterised by a semi-crystalline structure. From Fig. 1a, it can be scopy provides information regarding functional groups as well as the
clearly noted that CS possess a range of crystalline peaks. Regarding intermolecular interaction via analysis of FTIR spectra corresponding to
pure chitosan’s XRD pattern, two characteristic peaks at near 2θ° = 15° stretching or bending vibrations of particular bonds [47]. FTIR was
and 20° demonstrate the crystalline part of the pure chitosan mem- carried out in order to determine the shifting and variation in intensity
brane’s average intermolecular distance [39,40]. Chitosan’s rigid crys- of the bands due to functional groups in pure CS: PEO and CS: PEO:
talline structure is primarily kept through hydrogen bonding (both in- LiClO4 electrolyte samples. The literature reported that a key variable
termolecular and intramolecular), which is the product of amino and when determining a desired polymer host is the availability of het-
hydroxyl groups by means of an absorbed water molecule [41,42]. The eroatoms (e.g., O and N) that contain lone pair electrons [18]. More-
intermolecular hydrogen bonds can easily be disrupted as a result of over, it was reported in literature [5], that chain polymers in which the
blending of PEO with CS polymer. There is a clear lessening in the electro-negative atoms (i.e., oxygen or nitrogen) are present in their
crystalline peaks of pure CS compared to CS: PEO blend film. The XRD repeating units can act as solvents for a certain salt, which is attribu-
pattern for the selected samples of the blend electrolytes incorporated table to the complexation between cations and electro-negative atoms.
with LiCLO4 are shown in Fig. 2(a,b). It can be observed (see Fig. 2a) Moreover, studies have indicated that CS polymer is identified by a lone
that with addition of 20 wt% of LiClO4 salt, the crystalline peaks in amino group and a pair of hydroxyl groups in its repeat unit [48,49].

3
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

Fig. 2. XRD pattern for (a) CSPB2 and (b) CSPB4 blend electrolyte films.

Fig. 3(a,b) shows the FTIR spectra for pure CS:PEO and CS:PEO:LiClO4 resistance to the reactance [54]. Fig. 4(a–e) illustrates the electrical
complexes at various regions of infrared radiations. In the previous impedance plots (Zi vs Zr) for CS:PEO and CS:PEO:LiClO4 complexes.
work [50], it was observed that the broad peak at around 3559 cm−1 Clearly, with increasing salt concentration the bulk resistance (see the
associated with the eOH stretching and the strong peak at around insets) decreased. A noteworthy feature of the Figures is that a pair of
2900 cm−1 ascribed to the CeH stretching modes of PEO which are distinct regions predominates. First, a high frequency semicircle region
deeply affected by doping materials. In Fig. 3b, it is interesting to look arises from the solid electrolyte’s bulk effect; next a low frequency spike
at the peak resulted from C-H stretching (2904 cm−1) broadening with region arises due to electrode polarization (EP) (that is, the effect of
increasing LiClO4 to CS: PEO and almost disappeared at 40 wt% of blocking electrodes). EP occurs as a result of the emergence of electric
LiClO4 salt. The shift and reduction in intensity are indicators for the double layer (EDL) capacitances, which themselves arise from free
complex development between the dopant salt and CS:PEO. Each charge accumulation at the solid electrolyte and electrode surface in-
sample is linked with the primary absorption peaks features, containing terfaces [55]. Here, it is necessary for the complex impedance plots at a
vibration of amino group (NH2), O]CeNHR, and hydroxyl (OH) low frequency region to display a straight line parallel to the imaginary
functional groups of CS. In view of Fig. 3a, it is apparent that there are axis. In other words, while the straight line’s inclination ought to be
shifts to lower wave numbers in the amine (NH2), O]CeNHR and (OH) 90°, the blocking double-layer capacitance (EP phenomena) at the
groups bands, which is inductor for the complexation between the blocking electrodes brings about the inclination [56,57]. Table 1 lists
LiClO4 salt and CS: PEO [51,52]. Regarding the relative intensity of the the DC conductivity of pure CS:PEO and CS:PEO:LiClO4 electrolyte
bands, the lessening, broadening, and shifting in intensity are indicative samples at ambient temperature. It is interesting to note that the DC
for the electrostatic interaction between the functional groups of the CS: conductivity increased from 7.16 × 10−10 S cm−1 for pure CS:PEO to
PEO polymer blenders and the ions [53]. Moreover, the shift of vibra- 7.34 × 10−4 S cm−1 for CS:PEO incorporated with 40 wt% of LiClO4.
tional bands in the direction of lower wave numbers is indicative of the The low DC conductivity (high resistance, 4x106 Ohm) of pure CS:PEO
increasingly weak nature of the intermolecular and intramolecular reveals the insulating properties of polymers without dopant charge
hydrogen bonds that exist between polymer chains [49], and thus an carriers. Previous studies confirmed that polymer electrolytes with high
increase of amorphous phases. DC conductivity ranging from 10−5 to 10−3 S cm−1 are crucial for
electrochemical device applications including batteries and electrical
double layer capacitors (EDLCs) [23,24,38].
Impedance analysis Commonly, modeling and analysis of the spectra of impedance are
eased with an equivalent circuit, which stemmed from the fact that it is
The AC conductivity principle’s complex impedance spectroscopy a straightforward and offers the mechanism of the system [58].
measurements rely on assessments of cell impedance/admittance over Fig. 5(a,b) displays the experimental impedance plots with electrical
multiple frequencies, as well as the analysis of these in complex im- equivalent circuits (EEC) for chosen samples. The EEC model is fun-
pedance planes. As a comparatively thorough concept when considered damental to comprehend the electrical properties of polymer based
in relation to resistance, impedance is marked by the way in which it solid electrolytes. It is possible to represent experimental impedance
accounts for phase difference. In AC, the impedance (Z) is employed as plots using a three-component equivalent circuit. More specifically, the
opposed to the resistance, which can be computed by adding the

4
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

Fig. 3. FTIR spectra of (i) CS:PEO (pure film), (ii) CSPB1, (iii) CSPB2, (iv) CSPB3, and (v) CSPB4 in the region (a) 1450 cm−1 to 1800 cm−1, and (b) 2500 cm−1 to
4000 cm−1.

three principal components are ZCPE1, a constant phase element; frequency region under a rising concentration of salt (20 wt% of
ZCPE2, another constant phase element; and a bulk resistance (Rb) for LiClO4). Fig. 5a shows that the incomplete semicircle corresponds to Rb
the solid polymer electrolyte (see inset of Fig. 5a). Rb and ZCPE1 are in parallel with CPE element and in series with another CPE corre-
reflected in the high frequency region, whilst the low frequency spike sponding to low frequency tail (see the inset of Fig. 5a). Furthermore, at
region is connected to ZCPE2. This is indicative to the double layer 30 wt% and 40 wt% of LiClO4, the incomplete semicircle vanished
capacitance appearing at the interface between the electrodes and the completely (see Fig. 4(c-e), which indicates that it is feasible to consider
solid polymer electrolyte [59]. It is possible to derive ZCPE’s impedance merely the resistive behavior of the solid polymer electrolyte and the
as [60-62]: CPE component in series. A vital implication of the outcome is that the
semicircle vanished at the high frequency region of the impedance plot.
cos(πn/2) sin(πn/2)
ZCPE = −j Hence, the entire conductivity can be attributed to transportation of
Ym ωn Ym ωn (2)
ions [63]. In this case, the values of Zr and Zi associated to the EEC can
where Ym refers to the CPE capacitance, ω is the angular frequency and be expressed as:
n is correlated to the deviation of the plot from the vertical axis in cos(πn/2)
complex impedance plots. In particular, CPE is acronym commonly Zr = R +
Ym ωn (5)
applied instead of capacitor in the context of a modeled equivalent
circuit. The reason behind this is the behavior of solid polymer elec- sin(πn/2)
Zi =
trolytes differing from the behavior of an ideal or pure capacitor. This Ym ωn (6)
implies an ideal semi-circular pattern [59], which it is not possible to
identify in existing experimental impedance plots. In this case, it is
EDLC study
possible to express the real (Zr) and imaginary (Zi) complex impedance
(Z*) values in the equivalent circuit (insets of Fig. 5(a,b)) in the fol-
Increasing harmless electrolytes mainly solid polymer electrolytes
lowing way:
(SPEs) is an essential part of research for the application of electro-
R1 + R12 Y1 ωn1 cos(πn1/2) cos(πn2/2) chemical devices. Even though this compound system being initiated
Zr = Rs + + since late seventieth, it still believed one of the leading subjects
1 + 2R1 Y1 ωn1 cos(πn1/2) + R12 Y12 ω2n1 Y2 ωn2 (3)
[64,65]. To use the polymer electrolyte for application it is essential to
R12 Y1 ωn1 sin(πn1/2) sin(πn2/2) study the transference number analysis (TNM) and linear sweep vol-
Zi = + tammetry (LSV). In polymer electrolyte, it is crucial to determine the
1 + 2R1 Y1 ωn1 cos(πn1/2) + R12 Y12 ω2n1 Y2 ωn2 (4)
dominant charge carrier species, which can be done using TNM. The DC
It is obvious that the semicircle diameter shrunk at the high polarisation technique was employed to assess the sample’s ionic

5
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

Fig. 4. Experimental Impedance plots for (a) pure CS:PEO film (b) CSPB1, (c) CSPB2, (d) CSPB3, and (e) CSPB4 blend electrolyte films.

transference number (tion). The technique involves the application of maximum conductivity was positioned between a pair of stainless steel
DC voltage to the sample underneath its decomposition potential, blocking electrodes (SS) to ease the measurement, and it is likely to
which is followed by the examination of the resulting currents in re- employ the following equation to estimate both the ion (tion) and the
lation to time (see Fig. 6) [66]. The polymer electrolyte with the electron (tel) transference number:

6
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

Table 1 study. Moreover, it is likely to use the CV of EDLC cells to collect in-
DC conductivity for pure CS:PEO and blend electrolyte films at room formation about the charge storage nature at the single interfaces in the
temperature. cathodic and anodic regions [73]. In Fig. 8, the room temperature CV of
Sample Designation DC conductivity (S cm−1) the assembled cell is presented, with a notable finding being the lack of
a redox peak. This indicates that a non-Faradaic process has taken place
CS:PEO 7.16 × 10−10 in the current electrolyte system. Additionally, EDLC’s charge storage
CSPB1 6.18 × 10−7
mechanism relies on ion accumulation at the interfaces between elec-
CSPB2 3.02 × 10−5
CSPB3 1.63 × 10−4 trodes and electrolytes in the context of electric potential application
CSPB4 7.34 × 10−4 [74]. A noteworthy feature of Fig. 8, is that it is close to the ideal EDLC
which has an exact rectangular shape. The leaf-shaped pattern of CV
plot it means the system follows nearly rectangular shape [74,75]. Fast
Ii − Iss build-up of the electric double layer and internal resistance of EDLC are
tion =
Ii (7) often cited as the reasons for non-rectangular shapes. In the case of
internal resistance, this is reflected in a sudden voltage drop when
tion = 1 − tel (8) discharging the EDLC, also known as Vdrop (see charge–discharge
curve) [74,76,77]. Since the diagram of CV reveals no clear reversible
Here Iss is the steady-state current and Ii is the initial current. The Ii
humps, it is sensible to conclude that a fast Faradaic reversible reaction
is observed at 31µA. The large value of initial current is due to the
has not happened alongside the formation of the double layer [78].
contribution of both ion and electron at the initial stage. As the used
The electrochemical capacitance of materials can also be evaluated
electrodes are stainless steel which is known to block ions, thus a
by considering the cyclic discharge. Fig. 9 reveals the galvanostatic
drastic drop of current is noticed before constant at 0.20 µA [67]. This
charge–discharge curves of the assembled EDLC cells at ambient tem-
phenomenon depicts the ionic conductor behavior [68]. Since
perature for CS: PEO incorporated with 40 wt% of LiClO4. The dis-
tion = 0.993 and tel = 0.007, the outcome demonstrates that the ions are
charge curves show that the EDLC cells display linear characteristics,
the dominant charge carriers through the polymer electrolyte. The
indicative of excellent electrochemical performance from the EDLC
proximity of tion to 1, the ideal value, is a particularly noteworthy result,
[79]. Note worthily, the EDLC cells also display linear discharge be-
which indicates that the nature of the prepared electrolyte film’s
havior involving a small ohmic drop, thus suggesting a non-Faradic
transport mechanism is primarily ionic [66,69].
capacitive charge-storage mechanism [80]. Since the discharge curve’s
Another vital parameter that can be evaluated for the application
slope is presented as (x), the EDLC cells’ Cspe can be determined using
standpoint in electrochemical devices (e.g. supercapacitors) is the
the following equation:
working voltage range, frequently referred to as electrochemical sta-
bility [70]. The study used LSV, facilitated by stainless steel electrodes, i
to test the electrochemical stability of every polymer electrolyte, and Cspe =
xm (9)
Fig. 7 presents a typical LSV plot for the highest conducting CS:PEO:-
LiClO4 blend electrolyte. The outcomes indicate that, from the EDLC Here i is the applied current. Fig. 10 shows the Cspe versus cycle
application viewpoint [71], the electrochemical stability is in the sa- number. The capacitance value obtained from this current work is re-
tisfactory working voltage range of 2.24. Monisha et al. [72] reported latively higher than the previous literature. The maximum average Cspe
that the threshold voltage is that the current passes through the cells. is 6.88F g−1. This capacitance synthesized in the present work is of the
Shukur et al. [61] demonstrated a decomposition voltage of 2.10 V for great interest compared to the specific capacitance values of 2.6–3.0
lithium salt based biopolymer electrolyte. Thus, the potential stability, and 1.7–2.1 F g−1 which recorded for the EDLC cells with the Mg- and
i.e potential window of the relatively high conducting electrolyte in this Li-based PEO polymer electrolytes incorporated with ionic liquids [73].
work is suitable for energy storage device applications. It is clear that the capacitance almost constant over 100 cycles. While in
Cyclic voltammetric tests can be used to grow insight into the nature other reports huge reduction of Cspe was observed at large number of
of charge storage at the electrodes-electrolyte interfaces in the EDLC cycles. The researchers considered that ion aggregate formation could

Fig. 5. Experimental Impedance and EEC fitting plots for (a) CSPB2 and (b) CSPB4 blend electrolyte films.

7
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

Fig. 6. Variation of current with respect to time for the cell assembled with SS/[CS:PEO]:LiClO4/SS at an applied potential (ΔV) of 30 mV at ambient temperature.

be responsible for the diminishment of these electrochemical proper- the EDLC can be expressed as:
ties. In the case of the mobile ions, their preferences are to be ag-
gregated or paired up following the rapid charge and discharge pro- Vd
R esr =
cesses. Notably, it is probable for the ion pairs to block the ion i (10)
transportation of the polymer electrolyte, thus impacting the rate at
As seen in Fig. 9, there is a tiny voltage drop (Vd) prior each of the
which ions are adsorbed at the carbon pores. In turn, this lowers the
process of discharging. The voltage drop is gained in the range between
development of ion adsorption at the electrodes-electrolyte interfaces.
0.32 and 0.36 V which is because of the EDLC’s internal resistance.
In view of this, the energy and power density of the EDLC cells, and
Fig. 11 indicates the Resr values of the EDLC for 100 cycles. The Resr
their specific capacitance, are linked in an inversely proportional way
values of the EDLC ranges from 320 to 360 Ω. Electrolyte resistance,
to the number of cycles [81]. Other researchers reported for example
current collectors and the gap between current collector and electrolyte
4 F g−1, 4.3 F g−1, 8.4 F g−1 and 6.5–15 F g−1 for PEO9/LiCF3SO3
are the causes for internal resistance existence [83]. Low values of Resr
plasticized with 50 wt% PEG200 (PEO–NAPP)11/LiClO4, PVDF–HFD
reveal efficient contact between electrodes and electrolytes, evidencing
(25%) + PC10–EC10/LiClO4 Nafion 1100 ionomer swelled membranes,
the facility with which ion transportation towards the surface of the
Polyurethane8/LiClO4 and PVA– cellulose e–H3PO4 based electrolytes,
electrolyte can take place, therefore developing an electrical double-
respectively [82]. Thus, the outcome of Cspe is close to those reported in
layer [84]. The EDLC’s ESR for this research is not high when con-
literature for polymer based electrolytes doped with Li+ ion salts.
sidered in relation to the value associated with ionic liquid incorporated
The equivalent series resistance (Resr) is another crucial parameter
PEO-based polymer electrolyte (i.e., 1300 Ω) [73].
need to be identified to study the internal resistance of the EDLC. Resr of
The energy density (Ed) of the fabricated EDLC can be calculated via

Fig. 7. LSV curve for the cell with SS/[CS:PEO]:LiClO4/SS at scan rate of 50 mV s−1 at ambient temperature.

8
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

Fig. 8. CV plot of the assembled EDLC at 10 mV s−1 from 0 to 1 V.

Fig. 9. Galvanostatic charge–discharge performances of the EDLC cell over first 5 cycles.

the equation: V2
Pd =
4mR esr (12)
Cs V
Ed = −1
2 (11) Pd of the EDLC at the 1st cycle was 321 W kg and decreased to
311 W kg−1 at 5th cycle. The Pd values are detected to be in the range
Here V = 1 V. Fig. 12 illustrates that Ed at the 1st cycle is
between 302 and 321 W kg−1 from 10th to 100th cycle with average of
1.07 Wh kg−1. The Ed is then decreases to 1.04 Wh kg−1 and stabilized
305 W kg−1. As seen in Fig. 13, the Resr of the EDLC is nearly alike
at average of 0.94 Wh kg−1 from 10th cycle to 100th cycle. Hence, it
pattern with power density. At initial cycles the Resr values are observed
can be assumed that from 10th cycle to 100th cycle, the transportation
to raise and constant beyond 10th cycle where the Pd values reduce and
of ion possesses almost the same energy barrier [85]. The energy den-
gained stabilization after 10th cycle.
sity achieved for the EDLC cell in the present work is of great interest
compared to that reported (0.3 Wh kg−1) for ionic liquid incorporated
PEO based polymer electrolyte [73]. The energy density of the present Conclusions
work (0.94 Wh/kg) is small compared to the values (1.4 Wh/kg and
8.63 Wh kg−1) reported in our previous works [86,87], while it is Chitosan (CS):poly (ethylene oxide) (PEO):LiClO4 polymer blend
higher to that reported (0.86 Wh·kg−1) for Chitosan:Dextran in- electrolytes have been prepared and found to be possible for EDLC
corporated with LiClO4 salt [88]. Fig. 13 portrays the power density fabrication. The XRD analysis revealed that the crystalline peaks of CS
(Pd) of the fabricated EDLC which is calculated from the equation: decreased in CS:PEO host blend polymer due to the disruption of

9
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

Fig. 10. Specific capacitance (Cspe) of the assembled EDLC up to 100th cycle.

Fig. 11. Equivalent series resistance (Resr) of the assembled EDLC up to 100th cycle.

molecular hydrogen bonds. The hump intensity observed in the CS:PEO carbon electrodes surface. The average Cspe and Pd of the assembled
polymer blend electrolyte and reduced upon addition of LiClO4 salt. EDLC were 6.88F g−1 and 305 W kg−1, respectively. The Resr values
The FTIR analysis demonstrated the existence of complex development were in the range between 320 and 360 Ω where Ed stabilized at
between the CS:PEO and incorporated salt through the shifting and 0.94 Wh kg−1.
lessening in the FTIR bands intensity corresponding to functional
groups. The bulk resistance calculated from the impedance plots
dropped with increasing the concentration of the salt. The highest DC Acknowledgement
conductivity was measured to be 7.34 × 10−4 for CS:PEO doped with
40 wt% of LiCLO4 salt. With the high value of tion (0.993), ions have The authors gratefully acknowledge the financial support for this
been considered to be the main contributor in the ionic conduction study from Ministry of Higher Education and Scientific Research-
process in the polymer electrolytes. CS:PEO:LiClO4 system has been Kurdish National Research Council (KNRC), Kurdistan Regional
observed to be stable up to 2.24 V from LSV analysis. This threshold Government/Iraq. The financial support from the University of
voltage makes possible this system to be used in electrochemical de- Sulaimani and Komar Research Center (KRC), Komar University of
vices. There were no anodic and cathodic peaks emerged in the CV plot Science and Technology are greatly appreciated.
of the EDLC which indicates the redox reaction absence at the activated

10
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

Fig. 12. Energy density (Ed) of the assembled EDLC up to 100th cycle.

Fig. 13. Power density (Pd) of the assembled EDLC up to 100th cycle.

References [8] Salleh NS, Aziz SB, Aspanut Z, Kadir MFZ. Electrical impedance and conduction
mechanism analysis of biopolymer electrolytes based on methyl cellulose doped
with ammonium iodide. Ionics (Kiel) 2016;22:2157–67. https://doi.org/10.1007/
[1] Bhide A, Hariharan K. Ionic transport studies on (PEO)6:NaPO3 polymer electrolyte s11581-016-1731-0.
plasticized with PEG400. Eur Polym J 2007;43:4253–70. https://doi.org/10.1016/ [9] Senthil RA, Theerthagiri J, Madhavan J, Arof AK. Enhanced performance of dye-
j.eurpolymj.2007.07.038. sensitized solar cell using 2-mercaptobenzothiazole-doped poly(vinylidinefluoride-
[2] Li W, Yuan M, Yang M. Dual-phase polymer electrolyte with enhanced phase co-hexafluoropropylene) polymer electrolyte. Ionics (Kiel) 2016;22:1225–30.
compatibility based on Poly (MMA-g-PVC)/PMMA. Eur Polym J 2006;42:1396–402. https://doi.org/10.1007/s11581-016-1642-0.
https://doi.org/10.1016/j.eurpolymj.2005.12.015. [10] Theerthagiri J, Madhavan J. Organic dopant added polyvinylidene fluoride based
[3] Ndeugueu L, Aniya M. Structural characterization of the ac conductivity in Ag ion solid polymer electrolytes for dye-sensitized solar cells. J Phys Chem Solids
conducting glasses. J Mater Sci 2009;44:2483–8. https://doi.org/10.1007/s10853- 2016;89:78–83. https://doi.org/10.1016/j.jpcs.2015.11.003.
009-3318-x. [11] Senthil RA, Theerthagiri J, Madhavan J, Arof AK. Performance characteristics of
[4] Matabola KP, De Vries AR, Moolman FS, Luyt AS. Single polymer composites: a guanine incorporated PVDF-HFP/PEO polymer blend electrolytes with binary io-
review. J Mater Sci 2009;44:6213–22. https://doi.org/10.1007/s10853-009- dide salts for dye-sensitized solar cells. Opt Mater (Amst) 2016;58:357–64. https://
3792-1. doi.org/10.1016/j.optmat.2016.06.007.
[5] Stephan AM. Review on gel polymer electrolytes for lithium batteries. Eur Polym J [12] Senthil RA, Theerthagiri J, Madhavan J, Murugan K, Arunachalam P, Arof AK.
2006;42:21–42. https://doi.org/10.1016/j.eurpolymj.2005.09.017. Enhanced performance of dye-sensitized solar cells based on organic dopant in-
[6] Zhou S, Fang S. High ionic conductivity of all-solid polymer electrolytes based on corporated PVDF-HFP/PEO polymer blend electrolyte with g-C3N4/TiO2 photo-
polyorganophosphazenes. Eur Polym J 2007;43:3695–700. https://doi.org/10. anode. J Solid State Chem 2016;242:199–206. https://doi.org/10.1016/j.jssc.2016.
1016/j.eurpolymj.2007.06.001. 07.020.
[7] Kim JH, Won J, Kang YS. Olefin-induced dissolution of silver salts physically dis- [13] Senthil RA, Theerthagiri J, Madhavan J, Arof AK. Dye-sensitized solar cell using 4-
persed in inert polymers and their application to olefin/paraffin separation. J Memb chloro-7-nitrobenzofurazan incorporated polyvinyl alcohol polymer electrolyte.
Sci 2004;241:403–7. https://doi.org/10.1016/j.memsci.2004.05.027. Indian J Phys 2016;90:1265–70. https://doi.org/10.1007/s12648-016-0869-y.

11
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

[14] Hamsan MH, Shukur MF, Aziz SB, Kadir MFZ. Dextran from Leuconostoc me- [40] Aziz SB, Abidin ZHZ, Kadir MFZ. Innovative method to avoid the reduction of silver
senteroides-doped ammonium salt-based green polymer electrolyte. Bull Mater Sci ions to silver nanoparticles (Ag+ → Ago) in silver ion conducting based polymer
2019;3:57. https://doi.org/10.1007/s12034-019-1740-5. electrolytes. Phys Scr 2015;90:35808. https://doi.org/10.1088/0031-8949/90/3/
[15] Hirase R, Higashiyama Y, Mori M, Takahara Y, Yamane C. Hydrated salts as both 035808.
solvent and plasticizer for chitosan. Carbohydr Polym 2010;80:993–6. https://doi. [41] Wan Y, Creber KAM, Peppley B, Bui VT. Chitosan-based solid electrolyte composite
org/10.1016/j.carbpol.2010.01.001. membranes: I. Preparation and characterization. J Membr Sci 2006;280:666–74.
[16] Si Trung T, Thein-han WW, Thi N, Ng C-H, Stevens W. Functional characteristics of https://doi.org/10.1016/j.memsci.2006.02.024.
shrimp chitosan and its membranes as affected by the degree of deacetylation. [42] Aziz SB. Role of dielectric constant on ion transport : reformulated Arrhenius
Bioresour Technol 2006;97:659–63. https://doi.org/10.1016/j.biortech.2005.03. equation. Adv Mater Sci Eng 2016;2016:11. https://doi.org/10.1155/2016/
023. 2527013.
[17] Bai P, Cao F, Lan X, Zhao F, Ma Y, Zhao C. Chitosan gel beads immobilized Cu (II) [43] Smitha B, Sridhar S, Khan AA. Chitosan – sodium alginate polyion complexes as fuel
for selective adsorption of amino acids. J Biochem Biophys Methods cell membranes. Eur Polym J 2005;41:1859–66. https://doi.org/10.1016/j.
2008;70:903–8. https://doi.org/10.1016/j.jprot.2008.01.001. eurpolymj.2005.02.018.
[18] Lu G, Kong L, Sheng B, Wang G, Gong Y, Zhang X. Degradation of covalently cross- [44] Aziz SB, Abidin ZHZ, Arof AK. Effect of silver nanoparticles on the DC conductivity
linked carboxymethyl chitosan and its potential application for peripheral nerve in chitosan – silver triflate polymer electrolyte. Phys B Phys Condens Matter
regeneration. Eur Polym J 2007;43:3807–18. https://doi.org/10.1016/j.eurpolymj. 2010;405:4429–33. https://doi.org/10.1016/j.physb.2010.08.008.
2007.06.016. [45] Hashmi SA, Chandra S. Experimental investigations on a sodium-ion-conducting
[19] Ng LS, Mohamad AA. Protonic battery based on a plasticized chitosan-NH4 NO3 polymer electrolyte based on poly (ethylene oxide) complexed with NaPF6. Mater
solid polymer electrolyte. J Power Sources 2006;163:382–5. https://doi.org/10. Sci Eng, B 1995;34:18–26. https://doi.org/10.1016/0921-5107(95)01219-2.
1016/j.jpowsour.2006.09.042. [46] Sanders RA, Snow AG, Frech R, Glatzhofer DT. A spectroscopic and conductivity
[20] Khiar ASA, Puteh R, Arof AK. Conductivity studies of a chitosan-based polymer comparison study of linear poly (N -methylethylenimine) with lithium triflate and
electrolyte. Phys B Condens Matter 2006;373:23–7. https://doi.org/10.1016/j. sodium triflate. Electrochim Acta 2003;48:2247–53. https://doi.org/10.1016/
physb.2005.10.104. S0013-4686(03)00211-1.
[21] Osman Z, Ibrahim ZA, Arof AK. Conductivity enhancement due to ion dissociation [47] Dumitraşcu M, Meltzer V, Sima E, Vîrgolic M, Albu MG, Ficai A, et al.
in plasticized chitosan based polymer electrolytes. Carbohydr Polym Characterization of electron beam irradiated collagen-polyvinylpyrrolidone (pvp)
2001;44:167–73. https://doi.org/10.1016/S0144-8617(00)00236-8. and collagen-dextran (dex) blends. Dig J Nanomater Biostructures
[22] Buraidah MH, Teo LP, Majid SR, Arof AK. Ionic conductivity by correlated barrier 2011;6:1793–803.
hopping in NH4I doped chitosan solid electrolyte. Phys B Condens Matter [48] Agrawal P, Strijkers GJ, Nicolay K. Chitosan-based systems for molecular imaging.
2009;404:1373–9. https://doi.org/10.1016/j.physb.2008.12.027. Adv Drug Deliv Rev 2010;62:42–58. https://doi.org/10.1016/j.addr.2009.09.007.
[23] Kadir MFZ, Majid SR, Arof AK. Plasticized chitosan – PVA blend polymer electrolyte [49] Aziz SB, Abidin ZHZ. Electrical conduction mechanism in solid polymer electro-
based proton battery. Electrochim Acta 2010;55:1475–82. https://doi.org/10. lytes: new concepts to Arrhenius equation. J Soft Matter 2013;2013:1–8. https://
1016/j.electacta.2009.05.011. doi.org/10.1155/2013/323868.
[24] Subban RHY, Arof AK, Radhakrishna S. Polymer batteries with chitosan electrolyte [50] Aziz SB, Marif RB, Brza MA, Hassan AN, Ahmad HA, Faidhalla YA, et al. Structural,
mixed with sodium perchlorate. Mater Sci Eng, B 1996;38:156–60. https://doi.org/ thermal, morphological and optical properties of PEO filled with biosynthesized Ag
10.1016/0921-5107(95)01508-6. nanoparticles: new insights to band gap study. Results Phys
[25] Morni NM, Mohamed NS, Arof AK. Silver nitrate doped chitosan acetate films and 2019;13:102220https://doi.org/10.1016/j.rinp.2019.102220.
electrochemical cell performance. Mater Sci Eng, B 1997;45:140–6. https://doi. [51] Buraidah MH, Arof AK. Characterization of chitosan/PVA blended electrolyte doped
org/10.1016/S0921-5107(96)02023-5. with NH4I. J Non Cryst Solids 2011;357:3261–6. https://doi.org/10.1016/j.
[26] El-sawy NM, Abd El-rehim HA, Elbarbary AM, Hegazy EA. Radiation-induced de- jnoncrysol.2011.05.021.
gradation of chitosan for possible use as a growth promoter in agricultural pur- [52] Kadir MFZ, Aspanut Z, Majid SR, Arof AK. FTIR studies of plasticized poly (vinyl
poses. Carbohydr Polym 2010;79:555–62. https://doi.org/10.1016/j.carbpol.2009. alcohol)– chitosan blend doped with NH4NO3 polymer electrolyte membrane.
09.002. Spectrochim Acta Part A Mol Biomol Spectrosc 2011;78:1068–74. https://doi.org/
[27] Nagahama H, Maeda H, Kashiki T, Jayakumar R, Furuike T, Tamura H. Preparation 10.1016/j.saa.2010.12.051.
and characterization of novel chitosan/gelatin membranes using chitosan hydrogel. [53] Wei D, Sun W, Qian W, Ye Y, Ma X. The synthesis of chitosan-based silver nano-
Carbohydr Polym 2009;76:255–60. https://doi.org/10.1016/j.carbpol.2008.10. particles and their antibacterial activity. Carbohydr Res 2009;344:2375–82.
015. https://doi.org/10.1016/j.carres.2009.09.001.
[28] Koduru HK, Iliev MT, Kondamareddy KK, Karashanova D, Vlakhov T, Zhao X-Z, [54] Suvarna RP, Rao KR, Subbarangaiah K. A simple technique for a.c. conductivity
et al. Investigations on Poly (ethylene oxide) (PEO) - blend based solid polymer measurements. Bull Mater Sci 2002;25:647–51. https://doi.org/10.1007/
electrolytes for sodium ion batteries. J Phys Conf Ser 2016;764:1–8. https://doi. BF02707898.
org/10.1088/1742-6596/764/1/012006. [55] Venkateswarlu M, Satyanarayana N. AC conductivity studies of silver based fast ion
[29] Yang Y, Inoue T, Fujinami T, Mehta MA. Ionic conductivity and interfacial prop- conducting glassy materials for solid state batteries. Mater Sci Eng, B
erties of polymer electrolytes based on PEO and boroxine ring polymer. J Appl 1998;54:189–95. https://doi.org/10.1016/S0921-5107(98)00156-1.
Polym Sci 2002;84:17–21. https://doi.org/10.1002/app.10090. [56] Jacob MME, Prabaharan SRS, Radhakrishna S. Effect of PEO addition on the elec-
[30] Chun-guey W, Chiung-hui W, Ming-i L, Huey-jan C. New solid polymer electrolytes trolytic and thermal properties of PVDF-LiClO4 polymer electrolytes. Solid State
based on PEO/PAN hybrids. J Appl Polym Sci 2005;99:1530–40. https://doi.org/ Ionics 1997;104:267–76. https://doi.org/10.1016/S0167-2738(97)00422-0.
10.1002/app.22250. [57] Fonseca Jr CP, Cavalcante F, Amaral FA, Souza CAZ, Neves S. Thermal and con-
[31] Kim M, Lee L, Jung Y, Kim S. Study on Ion conductivity and crystallinity of com- duction properties of a PCL-biodegradable gel polymer electrolyte with LiClO4,
posite polymer electrolytes based on poly (ethylene oxide)/poly (acrylonitrile) LiF3CSO3, and LiBF4 salts. Int J Electrochem Sci 2007;2:52–63.
containing nano-sized Al2O3 fillers. J Nanosci Nanotechnol 2013;13:7865–9. [58] Pradhan DK, Choudhary P, Samantaray BK, Karan NK, Katiyar RS. Effect of plas-
https://doi.org/10.1166/jnn.2013.8107. ticizer on structural and electrical properties of polymer nanocompsoite electro-
[32] Jo G, Jeon H, Park MJ. Synthesis of polymer electrolytes based on poly(ethylene lytes. Int J Electrochem Sci 2007;2:861–71.
oxide) and an anion-stabilizing hard polymer for enhancing conductivity and cation [59] Mohapatra SR, Thakur AK, Choudhary RNP. Effect of nanoscopic confinement on
transport. ACS Macro Lett 2015;4:225–30. https://doi.org/10.1021/mz500717j. improvement in ion conduction and stability properties of an intercalated polymer
[33] Aziz SB, Abdullah RM. Crystalline and amorphous phase identification from the nanocomposite electrolyte for energy storage applications. J Power Sources
tanδ relaxation peaks and impedance plots in polymer blend electrolytes based on 2009;191:601–13. https://doi.org/10.1016/j.jpowsour.2009.01.100.
[CS:AgNt]x:PEO(x–1)(10≤x≤50). Electrochim Acta 2018;285:30–46. https://doi. [60] Aziz SB, Abdullah RM, Kadir MFZ, Ahmed HM. Non suitability of silver ion con-
org/10.1016/j.electacta.2018.07.233. ducting polymer electrolytes based on chitosan mediated by barium titanate
[34] Iro ZS, Subramani C, Dash SS. A brief review on electrode materials for super- (BaTiO3) for electrochemical device applications. Electrochim Acta
capacitor. Int J Electrochem Sci 2016;11:10628–43. https://doi.org/10.20964/ 2019;296:494–507. https://doi.org/10.1016/j.electacta.2018.11.081.
2016.12.50. [61] Shukur MF, Ithnin R, Kadir MFZ. Electrical characterization of corn starch-LiOAc
[35] Inagaki M, Konno H, Tanaike O. Carbon materials for electrochemical capacitors. J electrolytes and application in electrochemical double layer capacitor. Electrochim
Power Sources 2010;195:7880–903. https://doi.org/10.1016/j.jpowsour.2010.06. Acta 2014;136:204–16. https://doi.org/10.1016/j.electacta.2014.05.075.
036. [62] Teo LP, Buraidah MH, Nor AFM, Majid SR. Conductivity and dielectric studies of
[36] Zhang D, Zhang X, Chen Y, Yu P, Wang C, Ma Y. Enhanced capacitance and rate Li2SnO3. Ionics (Kiel) 2012;18:655–65. https://doi.org/10.1007/s11581-012-
capability of graphene/polypyrrole composite as electrode material for super- 0667-2.
capacitors. J Power Sources 2011;196:5990–6. https://doi.org/10.1016/j. [63] Rajendran S, Sivakumar P. Investigations on PVC/PAN composite polymer elec-
jpowsour.2011.02.090. trolytes. J Memb Sci 2008;315:67–73. https://doi.org/10.1016/j.memsci.2008.02.
[37] Pell WG, Conway BE. Peculiarities and requirements of asymmetric capacitor de- 007.
vices based on combination of capacitor and battery-type electrodes. J Power [64] Aziz SB, Kadir MFZ, Abidin ZHZ. Structural, morphological and electrochemical
Sources 2004;136:334–45. https://doi.org/10.1016/j.jpowsour.2004.03.021. impedance study of CS:LiTf based solid polymer electrolyte: reformulated Arrhenius
[38] Shukur MF, Ithnin R, Kadir MFZ. Protonic transport analysis of starch-chitosan equation for ion transport study. Int J Electrochem Sci 2016;11:9228–44. https://
blend based electrolytes and application in electrochemical device. Mol Cryst Liq doi.org/10.20964/2016.11.18.
Cryst 2014;603:52–65. https://doi.org/10.1080/15421406.2014.966259. [65] Aziz SB, Karim WO, Qadir KW, Zafar Q. Proton Ion conducting solid polymer
[39] Göktepe F, Çelik SÜ, Bozkurt A. Preparation and the proton conductivity of chit- electrolytes based on chitosan incorporated with various amounts of barium tita-
osan/poly (vinyl phosphonic acid) complex polymer electrolytes. J Non Cryst Solids nate (BaTiO3). Int J Electrochem Sci 2018;13:6112–25. https://doi.org/10.20964/
2008;354:3637–42. https://doi.org/10.1016/j.jnoncrysol.2008.03.023. 2018.06.38.

12
S.B. Aziz, et al. Results in Physics 15 (2019) 102584

[66] Tripathi M, Tripathi SK. Electrical studies on ionic liquid-based gel polymer elec- layer capacitors: comparative study with multiwalled carbon nanotubes and acti-
trolyte for its application in EDLCs. Ionics (Kiel) 2017;23:2735–46. https://doi.org/ vated carbon electrodes. J Phys Chem C 2012;116:26118–27. https://doi.org/10.
10.1007/s11581-017-2051-8. 1021/jp305128z.
[67] Kufian MZ, Aziz MF, Shukur MF, Rahim AS, Ariffin NE, Shuhaimi NEA, et al. PMMA [79] Fattah NFA, Ng HM, Mahipal YK, Numan A, Ramesh S, Ramesh K. An approach to
– LiBOB gel electrolyte for application in lithium ion batteries. Solid State Ionics solid-state electrical double layer capacitors fabricated with graphene oxide-doped
2012;208:36–42. https://doi.org/10.1016/j.ssi.2011.11.032. Ionic Liquid-Based Solid Copolymer Electrolytes. Materials (Basel) 2016;9:450.
[68] Diederichsen KM, Mcshane EJ, Mccloskey BD. Promising routes to a High Li+ https://doi.org/10.3390/ma9060450.
transference number electrolyte for lithium ion batteries. ACS Energy Lett [80] Das S, Ghosh A. Solid polymer electrolyte based on PVDF-HFP and ionic liquid
2017;2:2563–75. https://doi.org/10.1021/acsenergylett.7b00792. embedded with TiO2 nanoparticle for electric double layer capacitor (EDLC) ap-
[69] Amudha S, Suthanthiraraj SA. Silver ion conducting characteristics of a poly- plication. J Electrochem Soc 2017;164:1348–53. https://doi.org/10.1149/2.
ethylene oxide-based composite polymer electrolyte and application in solid state 0561713jes.
batteries. Adv Mater Lett 2015;6:874–82. https://doi.org/10.5185/amlett.2015. [81] Liew C, Ramesh S, Arof AK. Enhanced capacitance of EDLCs (electrical double layer
5831. capacitors) based on ionic liquid-added polymer electrolytes. Energy
[70] Pande GP, Kumar Y, Hashmi SA. Ionic liquid incorporated polymer electrolytes for 2016;109:546–56. https://doi.org/10.1016/j.energy.2016.05.019.
supercapacitor application. Indian J Chem 2010;49A:743–51http://hdl.handle.net/ [82] Shuhaimi NEA, Alias NA, Majid SR, Arof AK. Electrical double layer capacitor with
123456789/9673. proton conducting Κ -carrageenan – chitosan electrolytes. Funct Mater Lett
[71] Sampathkumar L, Selvin PC, Selvasekarapandian S, Perumal P, Chitra R, 2008;1:195–201. https://doi.org/10.1142/S1793604708000423.
Muthukrishnan M. Synthesis and characterization of biopolymer electrolyte based [83] Arof AK, Kufian MZ, Syukur MF, Aziz MF, Abdelrahman AE, Majid SR. Electrical
on tamarind seed polysaccharide, lithium perchlorate and ethylene carbonate for double layer capacitor using poly (methyl methacrylate)–C4BO8Li gel polymer
electrochemical applications. Ionics (Kiel) 2019;25:1067–82. https://doi.org/10. electrolyte and carbonaceous material from shells of mata kucing (Dimocarpus
1007/s11581-019-02857-1. longan) fruit. Electrochim Acta 2012;74:39–45. https://doi.org/10.1016/j.
[72] Monisha S, Mathavan T, Selvasekarapandian S, Benial AM, Latha MP. Preparation electacta.2012.03.171.
and characterization of cellulose acetate and lithium nitrate for advanced electro- [84] Asmara SN, Kufian MZ, Majid SR, Arof AK. Preparation and characterization of
chemical devices. Ionics (Kiel) 2016;23:2697–706. https://doi.org/10.1007/ magnesium ion gel polymer electrolytes for application in electrical double layer
s11581-016-1886-8. capacitors. Electrochim Acta 2011;57:91–7. https://doi.org/10.1016/j.electacta.
[73] Pandey GP, Kumar Y, Hashmi SA. Ionic liquid incorporated PEO based polymer 2011.06.045.
electrolyte for electrical double layer capacitors: a comparative study with lithium [85] Shukur MF. Characterization of ion conducting solid biopolymer electrolytes based
and magnesium systems. Solid State Ionics 2011;190:93–8. https://doi.org/10. on starch-chitosan blend and application in electrochemical devices Dissertation
1016/j.ssi.2011.03.018. Malaysia: University of Malaya; 2015.
[74] Winie T, Jamal A, Saaid FI, Tseng T. Hexanoyl chitosan/ENR25 blend polymer [86] Aziz SB, Hamsan MH, Karim WO, Kadir MFZ, Brza MA, Abdullah OGh. High proton
electrolyte system for electrical double layer capacitor. Polym Adv Technol conducting polymer blend electrolytes based on chitosan: dextran with constant
2018;30:726–35. https://doi.org/10.1002/pat.4510. specific capacitance and energy density. Biomolecules 2019;9(7):267. https://doi.
[75] Woo HJ, Liew C, Majid SR, Arof AK. Poly (ε-caprolactone)-based polymer electro- org/10.3390/biom9070267.
lyte for electrical double-layer capacitors. High Perform Polym 2014;26:637–40. [87] Hamsan MH, Abdullah RM, Kadir MFZ. A Promising polymer blend electrolytes
https://doi.org/10.1177/0954008314542168. based on chitosan: methyl cellulose for EDLC application with high specific capa-
[76] Kadir MFZ, Arof AK. Application of PVA – chitosan blend polymer electrolyte citance and energy density. Molecules 2019;24(13):2503. https://doi.org/10.3390/
membrane in electrical double layer capacitor. Mater Res Innov 2011;15:s217–20. molecules24132503.
https://doi.org/10.1179/143307511X13031890749299. [88] Shujahadeen BA, Hamsan Muhamad H. Development of polymer blend electrolyte
[77] Prabaharan SRS, Vimala R, Zainal Z. Nanostructured mesoporous carbon as elec- membranes based on chitosan: dextran with high ion transport properties for EDLC
trodes for supercapacitors. J Power Sources 2006;161:730–6. https://doi.org/10. application. Int J Mol Sci 2019;20(13):3369. https://doi.org/10.3390/
1016/j.jpowsour.2006.03.074. ijms20133369.
[78] Kumar Y, Pandey GP, Hashmi SA. Gel polymer electrolyte based electrical double

13