Electrochimica Acta 142 (2014) 359370

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Role of preparation methods on the structural and dielectric

properties of plasticized polymer blend electrolytes: Correlation
between ionic conductivity and dielectric parameters
R.J. Sengwa , Priyanka Dhatarwal, Shobhna Choudhary
Dielectric Research Laboratory, Department of Physics, Jai Narain Vyas University, Jodhpur342 005, India

a r t i c l e

i n f o

Article history:
Received 18 May 2014
Received in revised form 22 July 2014
Accepted 23 July 2014
Available online 8 August 2014
Keywords:
Polymer blend
Solid polymer electrolyte
Dielectric relaxation
Ionic conductivity

a b s t r a c t
The polymer blend based electrolyte lms consisted of poly(ethylene oxide) (PEO) and poly(methyl
methacrylate) (PMMA) with lithium triate (LiCF3 SO3 ) as a dopant ionic salt and poly(ethylene glycol)
(PEG) as plasticizer have been prepared by solution cast meltpressed and ultrasonic assisted followed
by microwave irradiated solution cast meltpressed methods. The Xray diffraction study infers that
the amorphous phase of (PEOPMMA)LiCF3 SO3 x wt% PEG electrolytes decreases with the increase of
PEG concentration. The complex dielectric function, ac electrical conductivity, electric modulus and the
impedance spectra of these electrolytes have been investigated over the frequency range from 20 Hz to
1 MHz. It is found that all the dielectric/electrical functions of these electrolytes vary anomalously with the
increase of PEG concentration, and also with the change of samples preparation methods. The activation
energies have been determined from the temperature dependent values of dc ionic conductivity, polymer
segmental relaxation time and dielectric strength. Results reveal that besides the amorphicity, the ionic
conductivity of these electrolytes is also governed by the relaxation time and the dielectric strength, and
the transport of ions is due to hopping mechanism which is coupled with segmental motion of polymers
chain. Room temperature ionic conductivity values of the PEOPMMA blend based electrolytes are found
about one to two orders of magnitude higher than that of the PEO and PMMA based electrolytes.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Solid polymer electrolytes (SPEs) have been recognized as the
most suitable exible type, leak proof and light weight novel materials for the fabrication of ion conducting devices particularly the
rechargeable batteries for portable electronic equipments [118].
The SPEs are complexes of polymer with cations of the dopant salt
and mostly have high amorphicity. But the low ionic conductivity
at ambient temperature limits their several technological applications. In these electrolytes the dynamics of polymer chains is
critical for the ions transportation. Therefore, the knowledge on
how the ions are coupled with the chain dynamics of the multiphase complex structures of the SPEs and the modication in these
structures with the preparation methods for the improvement of
ionic conductivity are nowadays prime issues [5,6,12,15,16,1921].
So far, enormous work is in progress on the SPE materials with
the choices of polymers and the alkali metal salts in order to achieve

Corresponding author. Tel.: +91 291 2720857; fax: +91 291 2649465.
E-mail address: rjsengwa@rediffmail.com (R.J. Sengwa).
http://dx.doi.org/10.1016/j.electacta.2014.07.120
0013-4686/ 2014 Elsevier Ltd. All rights reserved.

their high ionic conductivity ( 105 S cm1 ) at ambient temperature for the realistic device applications. Mostly, poly(ethylene
oxide) (PEO) matrix based complexes with various lithium salts
have been an intense eld of research [517,1930]. The PEO has
low lattice energy, low glass transition temperature, high solvating power for alkali metal salts and an ease to form exible type
lm. These facts make it an impending polymer in preparation of
the SPEs. But the high crystallinity of PEO is its main disadvantage
because effective ion transport can be achieved utmost in an amorphous medium of the host polymer. Besides the PEO, poly(methyl
methacrylate) (PMMA) matrix, which has amorphicity more than
96%, is also preferred in preparation of SPE materials [3,3138]. The
highly active electron donating carbonyl (C = ) functional group
of PMMA can easily coordinate with the cations of alkali metal
salts, which results in PMMAsalt complexes. Although PMMA has
light weight with high transparency, high strength and dimensional
stability, but its brittle property under a loaded force limits the
industrial and technological suitability of the PMMA based SPEs.
In the advancement of SPE materials, continuous work is in
progress on the PEOPMMA blend matrix based electrolytes to
overcome the drawbacks of the pristine polymers [3948]. The

360

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

advantages of this blend are; the addition of PEO in PMMA matrix

results in the increase of PMMA exibility and reduces its brittleness, whereas the PMMA environment increases the amorphous
phase of PEO. These properties of the PEOPMMA blend matrix have
been recognized its suitability as novel polymeric blend matrix of
tailormade properties for the preparation of SPEs. Our survey of
literature reveals that PEOPMMA matrix is used with lithium triate [39], lithium perchlorate [4045] and silver nitrate [4648]
as ion conducting salt with different plasticizers and inorganic
nanollers for the enhancement of the ionic conductivity of their
solution cast electrolyte lms. But the PEOPMMA matrix with
lithium triuoromethanesulfonate (lithium triate, LiCF3 SO3 ) as
ion conducting salt and poly(ethylene glycol) (PEG) as plasticizer
has not been studied for its possible applications in the advancement of ion conducting electrochromic devices. As compared to
the high dielectric constant plasticizers ethylene carbonate (EC)
s = 85.1 and propylene carbonate (PC) s = 69.0, at room temperature, the PEG has s = 22.1, which is very low. So it is interesting
to know how a low dielectric constant plasticizer affects the conductivity of the electrolytes. Further, PEG is a linear chain molecule
and its repeat unit is same as PEO backbone unit and therefore, how
the PEO structure varies with increase of PEG concentration, is also
interesting to study in these electrolytes.
In this paper, we have rst time prepared the PEOPMMA blend
matrix based electrolytes comprising LiCF3 SO3 salt and varying
concentrations of PEG by classical solution cast meltpressed and
ultrasonic assisted followed by microwave irradiated solution cast
meltpressed methods. The aim of ultrasound treatment is, rstly,
to enhance the PEOPMMA blend miscibility, and secondly to dissociate the salt clusters in the electrolyte solution, if present any.
The microwave irradiation is given to the solution with the aim
to modify the dipolar orientation and the PEG dynamics which
occur at microwave frequencies in the solutions. This study has
been carried out to explore the effects of sample preparation methods and plasticizer concentration on the dielectric properties, ionic
conductivity and structural dynamics of the SPE lms using dielectric relaxation spectroscopy. Further, an attempt has been made
to correlate the temperature dependent ionic conductivity to the
polymer chain dynamics (segmental relaxation) by tting the data
to the VogelTammanFulcher (VTF) equation of these polymer
electrolytes.

2. Experimental
2.1. Sample preparation
The PEO (Mw = 6 105 g mol1 ), PMMA (Mw = 3.5 105 g mol1 ),
PEG (Mw = 200 g mol1 ) and LiCF3 SO3 were obtained from
SigmaAldrich, USA. The anhydrous acetonitrile and tetrahydrofuran of spectroscopic grade were purchased from Loba Chemie,
India. The polymers and the salt were vacuum dried at 50 C for at
least 12 h before using. For the preparation of varying PEG concentrations (PEOPMMA)LiCF3 SO3 x wt% PEG electrolyte lms, the
50:50 w/w PEO:PMMA blend was used. The average molar ratio
9:1 was set for the total number of the ethylene oxide units (EO)
and the carbonyl groups (C = O) of the polymers blend to the lithium
cations (Li+ ) of the salt. The PEG concentrations x = 0, 5, 10 and 15
with respect to the weight of PEOPMMA blend were used.
Two different processing methods were used for preparation
of the electrolyte lms. (i) Classical solution casting (SC) method:
In this process, initially, the required amounts of PEO and PMMA
were dissolved in acetonitrile and tetrahydrofuran, respectively,
in separate glass bottles. After that LiCF3 SO3 was added in PEO
solution, and it was dissolved and mixed homogenously by magnetic stirrer. This PEO electrolyte solution was mixed with PMMA

solution which resulted in the polymer blend electrolyte solution.

Finally, the required amounts of PEG for different concentrations
were added into the PEOPMMA blend electrolyte solutions and
mixed homogeneously by magnetic stirring. Each PEG concentration homogenous solution was divided into two equal parts. The
rst parts were cast onto Teon petri dishes and by slow evaporation of solvent at room temperature, the solution cast (SC)
prepared (PEOPMMA)LiCF3 SO3 x wt% PEG lms were achieved.
(ii) Ultrasonic (US) assisted followed by microwave (MW) irradiated solution casting method: In this method, the second parts
of each polymeric electrolyte solutions of varying PEG concentrations, which were prepared as mentioned above, were sonicated by
ultrasonicator (250 W power, 25 kHz frequency) for 10 min duration with ONOFF step of 15 s. In this processing the stainless
steel sonotrode was directly immersed into the electrolyte solution for strong dose of the ultrasound. After that each of the solution
was irradiated by microwave electromagnetic energy in a domestic microwave oven (600 W power, 2.45 GHz frequency) for 2 min
duration and 10 s irradiation step with intermediate cooling. These
solutions were cast onto petri dishes which resulted in the USMW
irradiated solution cast lms after the solvents evaporation.
The surfaces of the solution cast lms prepared by above mentioned methods were found uneven. Therefore, the smooth surfaces
of these lms were achieved by meltpressed technique. In this
technique, each electrolyte lm was initially vacuum dried at 40 C
for 24 h. After that each lm was melted by heating it up to 130 C
in circular stainless steel die having suitable spacer using polymer
lm making unit. This melted material was pressed under 2 tons
of pressure per unit area and cooled slowly up to room temperature which made the lm of smooth surfaces. The same steps were
repeated for each lm.
2.2. Characterizations
The Xray diffraction (XRD) patterns of the SPE lms and their
constituents were recorded in reection mode using a PANalytical
operX pert Pro MPD diffractometer of Cu K radiation (1.5406 A)
ated at 45 kV and 40 mA with a scanned step size of 0.05 /s. The
powder sample of LiCF3 SO3 was tightly lled in the sample holder,
whereas the PEO, PMMA, PEOPMMA blend and the SPE lms were
placed on the top of sample holder during their XRD measurements
in the 2 range from 1030 at room temperature.
The dielectric relaxation spectroscopy (DRS) of the electrolyte
lms was carried out using Agilent technologies 4284A precision
LCR meter along with Agilent 16451B solid dielectric test xture in 1 V electric eld of linear frequency f range from 20 Hz
to 1 MHz at 30 C, and also with the temperature variation for
the 10 wt% PEG concentration lms. Frequency dependent values of capacitance Cp , resistance Rp and loss tangent (tan =  / )
of the SPE lms mounted in the dielectric cell were measured in
the parallel circuit operation for the determination of their dielectric/electrical spectra. Prior the sample measurement, the open
circuit calibration of the cell was performed to eliminate the effect
of stray capacitance of the cell leads. The dielectric test xture was
placed in a microprocessor-controlled heating chamber to record
the measurements at different temperatures. Initially, all the measurements of varying PEG concentrations electrolyte lms were
made at xed temperature, 30 C. After that the same lms of 10
wt% PEG concentration were used for their temperature dependence study from 3055 C. It was found that the re-measured values
of Cp , Rp and tan have good reproducibility after one week duration, which conrms that there is no immediate aging effect in
the studied electrolyte lms. The spectra of intensive quantities,
namely complex dielectric function * () =  j , real part of alternating current (ac) electrical conductivity   = 0  and electric
modulus M* () = M + jM , and the extensive quantity i.e. complex

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

361

(b) SC

(a)

0 wt%

PMMA

5 wt%
10 wt%
15

20

25

30

Intensity (a.u.)

Intensity (a.u.)

10

PEO
PMMA

15 wt%

US-MW

0 wt%
10 wt%

PEO-PMMA

15 wt%

LiCF3SO3

10

15

20

25

30

2 ( )

10

15

20

25

30

2 ( )

Fig. 1. XRD patterns of (a) PEO, PMMA and PEOPMMA blend lms, and LiCF3 SO3 powder; (b) (PEOPMMA)LiCF3 SO3 x wt% PEG electrolyte lms prepared by SC and
USMW methods.

impedance Z* () = Z jZ of the electrolyte lms were determined

using the expressions described in detail elsewhere [3,9].
3. Results and Discussion
3.1. Structural analysis
The XRD patterns of PEO, PMMA, PEOPMMA blend, LiCF3 SO3 ,
and the SC and USMW prepared (PEOPMMA)LiCF3 SO3 x wt%
PEG electrolytes over the angular range 1030 are shown in Fig. 1.
The XRD pattern of a material provides the structural properties
related to crystalline phases (peak positions), phase concentration (peak heights), amorphous content (back-ground hump) and
crystallite size (peak widths). The PEO peaks position 2 and the
corresponding intensity values of these materials are determined
by Xpert pro software and these values are given in Table 1. The
XRD pattern of pure PEO (Fig. 1(a)) has sharp crystalline peaks at
2 = 19.22 and 23.41 , which are corresponding to crystal reection planes 120 and concerted 112,032, respectively [8,15,49]. Inset
of Fig. 1(a) shows that PMMA has a broad and diffused peak around
16 , which conrms its predominantly amorphous phase [3]. The
PEOPMMA blend also has peaks at 19.19 and 23.33 which are
corresponding to PEO crystalline reection planes, but the intensities of these peaks are low as compared to pristine PEO (Table 1).
The relative low intensity peaks of PEOPMMA blend reveal that
there is some miscibility of PEO and PMMA which increases the
amorphous content, but some amount of PEO crystalline phase
also exists in the blend. The LiCF3 SO3 has intense crystalline peaks
at 16.62, 19.87, 20.53, 22.77 and 24.71 , which conrm its high
crystallinity. The angular positions and relative intensities of these
peaks are found in consistent with the earlier reported XRD spectra
of the LiCF3 SO3 [50].
The differences in XRD patterns of (PEOPMMA)LiCF3 SO3 x
wt% PEG lms prepared by SC and USMW processing methods
(Fig. 1(b)) conrm some structural variations due to the sample
preparation methods. The crystalline peaks of LiCF3 SO3 are not
found in the XRD patterns of these electrolytes, which infer that
the salt is completely dissociated due to formation of the cations

complexes with the functional groups of PEOPMMA blend. Further, the absence of PEO peaks in the USMW prepared lm and
a very low intensity peak in the SC prepared lm of the unplasticized (PEOPMMA)LiCF3 SO3 electrolyte infer that the formation
of iondipolar complexes has changed the polymer blend into
an amorphous material. Due to four to six coordination sites of
lithium cations with the oxygen atoms of PEO [10,22], and the
carbonyl groups of PMMA [32] and also formation of some miscible phase in the PEOPMMA blend result in complete amorphous
phase of the (PEOPMMA)LiCF3 SO3 electrolyte having the salt
concentration molar ratio [EO + (C = O)]:Li+ = 9:1. With the addition of PEG as plasticizer in these electrolytes both the peaks
of PEO have appeared, which conrm the recrystallization of a
small amount of PEO. The enhancement of PEO peaks intensities with the increase of PEG concentration of the electrolytes
(Table 1) is attributed to a gradual increase of crystalline phase
, because the peaks intensities are directly related with the material crystallinity [8,49]. In comparison to the SC prepared lms the
peak intensities of USMW prepared lms are low (Table 1), which
conrm that the high intensity ultrasonication disturbs the recrystallization of PEO. The end hydroxyl groups of PEG form the strong
intra- and inter-molecular hydrogen bonding [51]. It seems that
the hydroxyl groups of PEG form the ion-dipolar coordination with
the lithium cations which release some of the ether oxygen atoms
of PEO from the polymer-ion complexes. Due to this fact some
amount of uncomplexed PEO recrystallizes. As the PEG concentration increases in the electrolyte, more amount of PEO releases from
the complexes, which results in gradual increase of PEO crystalline
phase. Further, the presence of same unit in the backbone of PEG
and PEO molecules also favours the enhancement of PEO crystalline
phase as the PEG concentration increases in the PEOPMMA blend
based electrolytes. This structural nding of the PEG plasticized
electrolyte is very interesting, and so far this type of behaviour has
not been observed in other type of plasticizer added PEO based solid
polymer electrolytes [27,30,39,41,46]. Further, authors repeated
the XRD scans of some of the samples within one week duration,
and found good reproducibility of the scans which conrmed that
the samples did not suffer from immediate aging effect.

362

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

Table 1
Values of Braggs angles 2 and crystalline peak intensities I of pristine PEO lm, PEOPMMA blend lm, and (PEOPMMA)LiCF3 SO3 x wt% PEG electrolyte lms prepared
by SC and USMW methods.
2 1 ( )

x wt% PEG

2 2 ( )

I2 (counts)

12964

23.41

12569

4746

23.49

4800

329
1324
1326
1661

23.23
23.10
23.23

537
549
852

23.46
23.09

I1 (counts)

Pristine PEO lm
0
19.22
PEOPMMA blend lm
19.26
0
SC prepared (PEOPMMA)LiCF3 SO3 x wt% PEG electrolytes
19.34
0
19.12
5
18.99
10
15
19.11
USMW prepared (PEOPMMA)LiCF3 SO3 x wt% PEG electrolytes

0
19.24
10
18.88
15

402
1495

3.2. Dielectric and electrical behaviour

The complex permittivity (real part  and dielectric loss  )
spectra of (PEOPMMA)LiCF3 SO3 x wt% PEG electrolyte lms prepared through SC and USMW processes are shown in Figs. 2(a)
and 2(b), respectively. The  values of these electrolytes are in
the order of several thousands at low frequencies which decrease
nonlinearly with increasing frequency and approach the steady
state (high frequency limiting permittivity ) near 1 MHz, as
shown by the enlarged view in the inset of Fig. 2. The large  values of these polymeric electrolytes at low frequencies are due to
the electrode polarization (EP) effect occurring as a result of the
accumulation of ions near the electrodes surfaces of dielectric test
xture [9,10,15]. These  spectra have point of inection around
1 kHz, therefore the  values at this frequency are considered as
the static permittivity s of these electrolytes. The s and values of the polymeric electrolytes with PEG concentration are given
in Table 2. The values of dielectric strength  = s of these
materials are also recorded in Table 2.
As compared to the polymer matrix, the plasticizers have high
value of static permittivity. Therefore, by the algebraic additive rule,
it is expected that the increase of plasticizer concentration in the
polymeric electrolyte must increase the dielectric strength beside
the modication in material physical properties such as exibility, viscosity, microstructure, etc. Further, it is believed that the
increase of dielectric strength of the polymer electrolyte with the
addition of plasticizer must support the ion conduction process.
But the dielectric strength of a composite material is governed by
the dipolar ordering in its complex structure. The parallel dipolar
ordering increases the dielectric strength whereas it is reduced in
case of anti-parallel dipolar ordering. The comparison of Figs. 2(a)
and 2(b) and also the  values given in Table 2 reveals that
the  values of these electrolyte lms change anomalously with
the increase of PEG concentration and these values are also inuenced by the sample preparation methods. These results conrm

261
773

that there is signicant alteration in the strength of iondipolar

interactions and the dipolar ordering in the complexes with
increase of PEG concentration. The non-monotonous behaviour of
 with PEG concentration also reveals that the interaction of endhydroxyl groups of PEG with lithium cations and functional groups
of polymers makes them randomly aligned in the complexes, which
is also favoured by the changes in their crystalline phase (Table 1).
Figs. 2(c) and 2(d) show the temperature dependent  and 
spectra of the SC and USMW prepared (PEOPMMA)LiCF3 SO3 10
wt% PEG lms. It is found that both the  and  values increase
with increasing temperature, which is attributed to the increase
in charge density as an additional contribution from the interfacial polarization. The temperature dependent s , and  values
of the 10% PEG concentration electrolyte lm prepared by SC and
USMW methods are recorded in Table 3. It has also been revealed
that the magnitude of  values of these electrolyte lms follows
their  values. Further, each of the  spectrum has single relaxation
peak corresponding to the segmental motion (-relaxation) in the
miscible polymer blend. Due to large difference in the backbone
units of PEO and PMMA chains there must be separate relaxation
peaks in the  spectra on the frequency scale, but the appearance
of single relaxation peak also suggests a cooperative chain segmental dielectric relaxation process in these PEOPMMA blend based
electrolytes. The ColeCole plots ( vs  ) of the electrolyte lms
are shown in insets of the  spectra of Fig. 2. The high frequency
data in these plots has appeared as semicircular arcs corresponding
to the bulk properties whereas the low frequency data forms the
spikes due to dominance contribution of the EP effect in the low frequency dielectric properties. The  values of these electrolytes as
determined from their estimated s values are in consistence with
the other polymeric electrolytes which are determined by tting
the complex permittivity data to the HavriliakNegami function
[18].
The ac ionic conductivity  and the loss tangent tan spectra of
SC and USMW processed prepared (PEOPMMA)LiCF3 SO3 x wt%

Table 2
Values of static permittivity s , high frequency limiting permittivity , dielectric strength , loss tangent relaxation time tan , dc ionic conductivity dc , and fractional
exponent n of (PEOPMMA)LiCF3 SO3 x wt% PEG electrolyte lms prepared by SC and USMW methods.
x wt% PEG

SC prepared (PEOPMMA)LiCF3 SO3 x wt% PEG electrolytes

2820.9
14.8
0
4463.9
16.7
5
3060.4
13.9
10
1365.1
18.8
15
USMW prepared (PEOPMMA)LiCF3 SO3 x wt% PEG electrolytes
3478.4
8.0
0
2255.3
12.9
10
2562.4
14.2
15

tan
(s)

dc 105
(S cm1 )

2806.1
4447.2
3046.5
1346.3

1.40
1.19
1.21
0.35

1.01
1.46
1.09
1.62

0.91
0.92
0.88
0.96

3470.4
2242.4
2548.2

0.34
0.93
1.03

2.02
1.07
1.19

0.92
0.89
0.90

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

363

(b)

(a)

8000

200

120

8000
100

'

'

60

4000

6000

''

4000
2000

2000

''

''

''

4000

3000 6000

10

x wt% PEG
0
10
15

3000
0

10

4000

10

x wt% PEG
0;
5
10;
15

4000

10

2000

2000 4000

'

'

(d)

(c)
10000

200

8000

200

100

'

'

100
0

5000

4000

10

30 C

10

35 C

45 C

55 C

55 C

''

4000

3000

''

4000

2000

2000

4000

'

2000
0

''

''

4000

6000

10

35 C

45 C

10
30 C

2000

2000

4000

'

0
1

10

10

10

10

10

10

f (Hz)

10

10

10

10

10

10

f (Hz)

Fig. 2. Frequency dependent real part  and loss  of the complex dielectric function of (a) SC prepared and (b) USMW prepared (PEOPMMA)LiCF3 SO3 x wt% PEG lms
at 30 C; and (c) SC prepared (d) USMW prepared (PEOPMMA)LiCF3 SO3 10 wt% PEG lms with temperature variation.

PEG electrolytes are depicted in Figs. 3(a) and 3(b), respectively.

The  values of these polymeric electrolytes increase nonlinearly
with increase of frequency on logarithm scale. It has been established that the ion transportation in polymeric electrolytes occurs
on different time scale under the inuence of alternating current
(ac) electric eld [8,17,18,52,53]. The jumps of ions between different ion sites through hopping mechanism are demonstrated
by random barrier model which consequences the ac conductivity dispersion [52]. The shorttime ion dynamics is characterized
by backandforth motion over the limited range in disordered
polymer matrix, subdiffusive dynamics, which leads to dispersive ac conductivity at high frequencies. Whereas the longtime ion
dynamics is characterized by random walks resulting in longrange
ion transport, diffusive dynamics, which leads to the plateau corresponding to the direct current (dc) ionic conductivity at frequencies
lower than that of the dispersive ac conductivity region. The dc

conductivity of such electrolytes mostly obeys the Arrhenius temperature dependent behaviour [7,17]. The ac conductivity of the
polymeric electrolytes also obeys timetemperature superposition,
i.e. it is possible to scale data at different temperatures to one single master curve which is roughly same for all disorder materials
[18,52,54]. Further, at high frequencies, the loglog plot of ac conductivity follows apparent power law behaviour [55]. Therefore the
detailed studies of frequency dependent ac conductivity behaviour
of SPEs have academic interest, besides the conrmation of their
suitability for technological applications.
The  spectra of the investigated electrolytes show three
regions on frequency scale; (i) the electrode polarization dominated low frequency region below 10 kHz, (ii) the dc plateau region
above 30 kHz up to nearly 300 kHz, and (iii) the power law dispersive region above 300 kHz. The values of dc ionic conductivity dc
of these electrolytes are determined by tting the  spectra above

364

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

(a)

(b)
-5

-5

-1

' (S cm )

10

-1

' (S cm )

10

-6

10

-6

10

-7

10

-7

10
-8

10

x wt% PEG
0
5
10
15

4.5

tan

tan

3.0

x wt% PEG
0
10
15

1.5

2
0

0.0

(c)

(d)
-5

10

' (S cm )

-1

-1

' (S cm )

-5

10

-6

10

-6

10

-7

10
-7

10

4.5

5.0

30 C

30 C
o

35 C

35 C

45 C

55 C

3.0

tan

tan

45 C

55 C

2.5

1.5

10

10

10

10

10

10

f (Hz)

0.0

10

10

10

10

10

10

f (Hz)

Fig. 3. Frequency dependent real part of ac conductivity and loss tangent (tan) of (a) SC prepared and (b) USMW prepared (PEOPMMA)LiCF3 SO3 x wt% PEG lms at
30 C; and (c) SC prepared (d) USMW prepared (PEOPMMA)LiCF3 SO3 10 wt% PEG lms with temperature variation.

30 kHz to the conventional Jonschers power law  () = dc + An

[55], where A is the preexponential factor and n is the fractional
exponent ranging between 0 and 1. These ts are shown by solid
lines in the  spectra. Further, it is observed that the  increases
with the increasing temperature of the electrolytes (Figs. 3(c) and
3(d)). This increase has two implications, rstly, the mobility of the
ions increases due to increased polymer chain segmental motion,
and secondly, the ion concentration increases. But the XRD spectra reveals that the total salt is in dissociated form and hence the
increase of temperature does not have any additional effect in dissociating the salt. This fact conrms that the increase of  values
of these electrolytes is due to increase of ions mobility only. Further, the presence of small salt clusters of nm size is also ruled out
because the salt concentration is not very high. The evaluated values of dc and n of the electrolytes with the PEG concentration and
the temperature variation are given in Tables 2 and 3, respectively.
The n values of the electrolytes are found in the range from 0.88

to 0.98, which suggests that the ions transportation in these electrolyte also takes place through hopping mechanism as reported
for other polymeric electrolytes [10,15,17,18,52,56]. Further, it is
found that the n values of the electrolyte increase with increase
of temperature (Table 3). This agrees well with the idea that n
physically represents the strength of the ionion and iondipolar
interactions and as the temperature increases these interactions
are expected to decrease [25].
The tan spectra of the electrolytes shown in Fig. 3 have Debye
type relaxation peaks appearing in the dc plateau frequency region
of the  spectra. The Debye-type relaxation peak suggests the transient behaviour of the complex structures of these electrolytes.
Therefore, these peaks represent the polymers segmental dynamics of the complexed miscible blend. The intensities of these peaks
vary with the PEG concentration and also with the sample preparation methods (Figs. 3(a) and 3(b)). But the tan peak intensity has
an increase with increase of temperature and also shifts towards

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

(a)

365

(b) 0.02

0.018

M'

M'

0.012

0.01

0.006

0.00

0.000
x wt% PEG
0
5
10
15

M''

0.02

0.03

35 C
o

55 C

0.01

0.00

0.00
1

10

45 C

0.02

0.01

10

30 C

M''

0.03

10

10

10

10

f (Hz)

10

10

10

10

10

10

f (Hz)

Fig. 4. Frequency dependent real part M and loss M of complex electric modulus of (a) SC prepared (PEOPMMA)LiCF3 SO3 x wt% PEG lms at 30 C; and (b) SC prepared
(PEOPMMA)LiCF3 SO3 10 wt% PEG lm with temperature variation.

higher frequency side (Figs. 3(c) and 3(d)) which infers that the
polymer dynamics in the complexed structures of the electrolyte
increases. The relaxation time tan corresponding to these polymer
blend segmental motion of the complexed structures is determined
by the relation tan = 1/2fp(tan) , where fp(tan) is the frequency
corresponding to tan peak. The observed tan values of the electrolytes are given in Tables 2 and 3 with PEG concentration and the
temperature variation, respectively. Table 2 shows that the tan
values of SC prepared lms are nearly same (except 15 wt% PEG).
But in case of USMW prepared lms the tan value of 0 wt% PEG is
found signicantly different as compared to the 10 and 15 wt% PEG
concentrations. Interestingly, it is also observed that the tan value
of SC prepared 15 wt% PEG is same as that of USMW prepared 0
wt% PEG electrolyte lm and these values are relatively very low.
It is observed that the (PEOPMMA)LiCF3 SO3 10 wt% PEG electrolyte lms prepared by both the methods have decrease of tan
values with the increase of temperature (Table 3) conrming the
increase of polymer dynamics in their complexes.
Figs. 4(a) and 4(b) show the electric modulus (real part M and
loss M ) spectra of the SC prepared (PEOPMMA)LiCF3 SO3 x wt%
PEG electrolyte lms of different PEG concentration and the 10 wt%
PEG concentration lm at varying temperatures, respectively. Similar types of M and M spectra are also observed for the USMW
prepared lms. These spectra are free from the contribution of EP
effect, and independent of the nature of electrode material, the electrode/dielectric specimen contact, and the adsorbed impurities in
the sample. The M and M spectra of these electrolytes have dispersion above 100 kHz, whereas in the EP effect dominated frequency
region their values are found close to zero because of the product M*()*() = 1. Mostly, the M spectra of the ion conducting
electrolytes exhibit a peak corresponding to the ionic conductivity
relaxation time [2,10,15,17,46,53,56]. But in these electrolytes the
M spectra peaks seem to appear above the upper limit of the experimental frequency range. With an increase of temperature, the M
dispersion has shift towards higher frequency side which reveals
that the ionic relaxation is thermally activated with the hops of
charge carriers.

The Nyquist impedance plots (Z vs Z ) of the

(PEOPMMA)LiCF3 SO3 x wt% PEG electrolyte lms prepared
through SC and USMW processes are depicted in Figs. 5(a) and
5(b), respectively. These plots are widely used for the electrochemical characterization of the ion conducting electrolyte materials.
The nature of charge carriers (electrons or ions), the frequency
range over which the EP effect contributes in bulk properties, the
behaviour of electrodeelectrolyte contact, and the dc resistance
and the dc ionic conductivity of the electrolytes are generally
analyzed from these plots [2,4,12,18,34,37,41]. The ion conducting
polymeric electrolyte materials commonly exhibit a spike in the
low frequency region and an arc in the high frequency region of
their Z vs Z plots. The insets of Figs. 5(a) and 5(b) show the similar
behaviour of the studied polymeric electrolytes. The spike of an
ideal capacitive element should be parallel to the imaginary axis,
but for the studied electrolyte it deviates from ideal behaviour
which is due to irregularities at the electrode/electrolyte contact.
The interfacial impedance for such materials can be described
by a constant phase element (CPE). In the parallel equivalent
circuit consisting of bulk resistance Rb in parallel with geometrical
capacitance Cg , the CPE acts in series as shown in inset of Fig. 5(b).
The common intercept of the arc and the spike line on the real
axis gives the bulk resistance Rb value of the electrolyte lm
[2,12,18]. Further, the frequency value corresponding to this
intercept point separates the bulk and EP affected frequency
region of the electrolyte material [24,9,17]. The dc values of
the ion conducting electrolyte lm can also be determined using
the relation dc = tg /Rb A, where tg is the thickness and A is the
surface area of the lm. In the present study, the dc values of the
investigated electrolyte lms are determined by power law t to
the spectra, which are found nearly same as those evaluated using
Rb values. Figs. 5(c) and 5(d) show the temperature dependent
Z vs Z plots of (PEOPMMA)LiCF3 SO3 10 wt% PEG electrolytes
prepared through SC and USMW methods, respectively. The
insets show that these plots have shift towards low resistance side
on the real axis which conrms the decrease of their Rb values
with increase of temperature.

366

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

(a)

(b)

25

20

x wt% PEG
0
5
10
15

15

x wt% PEG
0
10
15

Cg

Z" (k )

Z" (k )

CPE

15

10

0.2

10

Rb
0.2

5
0.1

0.1

0.0
0.1

0
0

10

0.2

15

0.3

20

25

0.1 0.2 0.3

12

15

(d)

(c)

30 C

30 C
o

35 C

16

35 C

45 C

55 C

45 C

55 C

Z" (k )

Z" (k )

12

0.2

0.1

0.2

0.1

0.0

0.1

0.2

0.3

0
0

12

16

Z' (k )

0
0

0.1

10

0.2

15

0.3

20

Z' (k )

Fig. 5. Complex impedance plane plots (Z vs Z ) of (a) SC prepared and (b) USMW prepared (PEOPMMA)LiCF3 SO3 x wt% PEG lms at 30 C; and (c) SC prepared (d)
USMW prepared (PEOPMMA)LiCF3 SO3 10 wt% PEG lms with temperature variation.

3.3. Correlation between ionic conductivity and dielectric

parameters
Fig. 6 shows the variation of the room temperature (RT)
, tan and dc values with the PEG concentration of
(PEOPMMA)LiCF3 SO3 x wt% PEG electrolyte lms prepared by
SC and USMW methods. Fig. 6 has been plotted in order to
identify the dependence of ionic conductivity on the dielectric
parameters of these electrolytes. It has been established that for
the solid polymeric electrolytes, the dc value increases with the
increase of dielectric strength and also with the decrease of polymer chain segmental motion relaxation time [7,10,15,17,18,46,56].
In such electrolytes the transportation of ions occurs due to segmental motion of cations coordinated polymer chain [25,36,4345].
It is found that the dc value of USMW prepared lm is two
times higher than that of the SC prepared lm at 0 wt% PEG
(Table 2). This conrms that the USMW processing is effective

for the enhancement of ionic conductivity of the unplasticized

(PEOPMMA)LiCF3 SO3 electrolyte. This increase in conductivity
is also favoured by the high  and low tan values of the USMW
electrolyte lm as compared to that of the SC prepared unplasticized electrolyte lm (Fig. 6). Further, it is observed that the dc
values of the plasticized electrolytes at a xed PEG concentration
are also governed by their  and tan values. The dc values of
SC prepared plasticized electrolytes are found higher than that of
without plasticizer added electrolytes, and these values have a nonmonotonous behaviour with the PEG concentration. But in case of
USMW prepared electrolytes, the dc values of plasticized electrolytes are found lower than that of the unplasticized electrolytes.
The contribution of PEG plasticizer is found insignicant in the
enhancement of ionic conductivity of (PEOPMMA)LiCF3 SO3 x
wt% PEG electrolytes prepared by USMW method, which is
expected because PEG increases the crystalline phase of polymeric
electrolytes as revealed from their XRD patterns.

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

367

8x10
3
6x10

5x10
3
4x10
3
3x10

4x10

2x10

2x10

SC
US-MW

SC
US-MW

tan

(s)

10

1.0

tan

(s)

10
1.5

-1

10
-1

(S cm )
dc

2.0

-5

3x10

-5

1.5

10

dc

-1

x 10 (S cm )

0.5

1.0

3.1

3.2

3.3

-1
1000/T (K )

0.5
0

10

15

x wt % PEG
Fig. 6. PEG concentration dependent dielectric strength , loss tangent relaxation time tan and dc ionic conductivity dc of (PEOPMMA)LiCF3 SO3 x wt% PEG
electrolyte lms prepared by SC and USMW methods.

Here, it is worthy to compare the dc values of

the (PEOPMMA)LiCF3 SO3 with the PEOLiCF3 SO3 and
PMMALiCF3 SO3 electrolytes at RT in order to explore the
effect of PEOPMMA blending. The reported dc values of
PEOLiCF3 SO3 are 107 108 S cm1 [7], 3.5 107 S cm1 [22],
2 109 S cm1 [23], 3.5 107 S cm1 [24], 107 S cm1 [25],
3 108 S cm1 [28] and 3.8 107 S cm1 [29], which are in the
range of 107 109 S cm1 . The variations in these values are
due to the differences in salt concentration of the electrolytes,
the sample preparation methods and the evaluation of the experimental data. These values have further increased by one to two
orders of magnitude with the addition of ethylene carbonate
(EC) and propylene carbonate (PC) as plasticizers [24,27,30], and
also alumina (Al2 O3 ), silica (SiO2 ) and organomodied montmorillonite (MMT) clay as inorganic nanoller [2224]. Survey of
literature reveals that the dc values of PMMALiCF3 SO3 at RT are
2.29 106 S cm1 [36] and 1.16 106 S cm1 [37], which are
also increased by one to two orders of magnitude with the addition
of EC and PC plasticizers [35,37]. But the dc values of the investigated (PEOPMMA)LiCF3 SO3 x wt% PEG electrolytes at RT are
105 S cm1 , which are about two to three orders of magnitude
higher than that of the PEOLiCF3 SO3 electrolytes, and nearly one
order of magnitude higher than the PMMALiCF3 SO3 electrolytes.
This nding also suggests that the PEOPMMA blending results
in increase of their ionic conductivity up to the same order of
the magnitude as that of plasticized PEO and PMMA electrolytes,
which is very interesting and conrms its suitability as a novel
solid polymer electrolyte for the lithium ion rechargeable batteries
and the other electrochromic devices. It has also been conrmed
that the PEG plasticizer has less effect on the increase of ionic
conductivity of these electrolytes, which may be due to the facts
that PEO itself acts as plasticizer for the PMMA in the PEOPMMA
blend and also there is a complete dissociation of the salt in the
blend matrix.

Fig. 7. Reciprocal temperature dependence of dielectric strength , loss tangent

relaxation time tan and dc ionic conductivity dc of (PEOPMMA)LiCF3 SO3 10
wt% PEG electrolyte lms prepared by SC and USMW methods.

Fig. 7 shows the temperature dependent , tan and dc

values of the (PEOPMMA)LiCF3 SO3 10 wt% PEG lms prepared by SC and USMW methods. On logarithmic scale these
parameters have almost linear variation with reciprocal of temperature which conrm their Arrhenius behaviour. These plots
infer that the temperature dependent dc values are also governed by their corresponding  and tan values. The decrease
of tan values favors the increase of dc values which is also supported by the increase of  values with increasing temperature of
these materials. Mostly, the PEO based electrolytes have increase
of their dc values by one to two orders of magnitude when the
temperature increases and exceeds the PEO melting temperature
[7,13,22,24,29]. Due to increase of temperature the viscosity of electrolyte decreases and nally the material changes into amorphous
phase, which results in increase of free volume and favourable ion
conducting paths in thermally activated dynamical medium. In the
present study, the temperature dependent conductivity study has
been carried out only in the temperature range of 3055 C in order
to determine the activation energies of these polymers blend electrolytes.
The conductivity activation energy E and dielectric relaxation
time activation energy E of the (PEOPMMA)LiCF3 SO3 10 wt%
PEG electrolytes have been determined by the Arrhenius relations
dc = 0 exp(E /kT) and tan = 0 exp(E /kT), respectively. On the
compressed scale, the dc and tan versus 1000/T plots are linear.
The slopes of these plots were used for the determination of activation energies. The obtained values of activation energies are listed
in Table 4. Because of the linear behaviour of  versus 1000/T
plots, the dielectric strength activation energy E values are also
determined using similar type of Arrhenius relation, and these are
also given in Table 4. The E and E values of the SC prepared electrolyte lm are found slightly higher as compared to the USMW
prepared lm of the same composition material. Further, it is found
that for these electrolytes the E values are a little higher than the
respective E values. The observed E values are found in consistent with the other polymeric electrolytes [7,17,18,45]. The low
activation energy values of these electrolytes suggest that there is

368

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

Table 3
Temperature dependent values of static permittivity s , high frequency limiting permittivity , dielectric strength , loss tangent relaxation time tan , dc ionic conductivity
dc , and fractional exponent n of (PEOPMMA)LiCF3 SO3 10 wt% PEG electrolyte lms prepared by SC and USMW methods.
Temperature ( C)

SC prepared (PEOPMMA)LiCF3 SO3 10 wt% PEG electrolyte

30
3060.4
13.9
35
3293.0
15.0
3663.9
15.6
45
55
4613.1
16.3
USMW prepared (PEOPMMA)LiCF3 SO3 10 wt% PEG electrolyte
2255.3
12.9
30
2429.0
13.0
35
45
2758.3
13.5
3391.8
15.0
55

tan (s)

dc 105 (S cm1 )

3046.5
3278.0
3648.3
4596.8

1.21
1.16
0.81
0.40

1.09
1.19
1.64
2.66

0.88
0.89
0.93
0.98

2242.4
2416.0
2744.8
3376.8

0.93
0.90
0.68
0.41

1.07
1.13
1.57
2.12

0.89
0.90
0.90
0.97

Table 4
Values of conductivity activation energy E , relaxation time activation energy E and dielectric strength activation energy E of (PEOPMMA)LiCF3 SO3 10 wt% PEG electrolyte
lms prepared by SC and USMW methods.
Electrolyte preparation methods

E (eV)

E (eV)

E (eV)

SC
USMW

0.27
0.22

0.33
0.25

0.12
0.12

Table 5
The VTF tted parameters from the temperature dependence of the dc ionic conductivity and the dielectric relaxation time of (PEOPMMA)LiCF3 SO3 10 wt% PEG electrolyte
lms prepared by SC and USMW methods.
Electrolytes preparation methods

VTF t
1

0 (S cm

VTF t
)

3.00 107
1.70 107

SC
USMW

Ev (eV)

T0 (K)

0 (s)

Ev (eV)

T0 (K)

0.315
0.857

351.07
379.50

1.97 106
1.40 106

0.155
0.137

339.22
340.85

relatively fast hopping mechanism for the ions, which is because

of the thermally activated transient coupling between the mobile
cations and the dynamical chain segmental structures of the polymers. A little difference in E and E values of these electrolytes also
infers that the ion transportation occurs through hopping mechanism, and the ions have to overcome the same barrier while relaxing
as well as while conducting, as reported for the PEO based electrolytes [17,53]. This fact suggests that in ion transportation both

1.5x10
-6

tan

(s)

10

-7

SC
US-MW
VTF fit
VTF fit

-1

(S cm )

5x10

-5

dc

2x10

the segmental motion of polymer chain and hopping motion contribute equally in coupled form for the (PEOPMMA)LiCF3 SO3 10
wt% PEG electrolyte.
To have better insight into the temperature dependence of tan and dc values, the experimental data of
(PEOPMMA)LiCF3 SO3 10
wt%
PEG
electrolytes
prepared by SC and USMW methods have been tted to the
VogelTammanFulcher (VTF) equations tan = 0 exp(Ev /k(TT0 ))
and dc = 0 T1/2 exp(Ev /k(TT0 )), respectively. In the VTF relations, 0 and 0 are the pre-exponential factors, Ev is the
pseudo-activation energy and T0 is the equilibrium glass transition
temperature. Although, the measurements in the present study
are in narrow temperature variation range (3055 C), but on
the enlarged scale, these tan and dc versus 1000/T plots tted
to the VTF equation have curved shape (Fig. 8) which conrms
the presence of free volume in the investigated electrolyte lms.
The VTF tted parameters 0 , 0 , Ev and T0 are listed in Table 5.
The T0 values of the PEOPMMA (50/50 wt%) based electrolytes
were found in good agreement to those reported earlier for the
PEOPMMA blend (20/80 wt%) based electrolytes [44]. Further, the
reasonably good t of temperature dependence tan and dc data
demonstrates the coupling between the ionic conductivity and
segmental relaxation in the PEOPMMA blend based electrolytes
as established in earlier studies [25,45].
4. Conclusions

-5

10

3.1

3.2

3.3

-1
1000 / T (K )
Fig. 8. Temperature dependent plots of the relaxation time and the ionic conductivity of (PEOPMMA)LiCF3 SO3 10 wt% PEG electrolyte lms prepared by SC and
USMW methods. The continuous lines show the t of experimental data to the VTF
equations.

The detailed dielectric dispersion and electrical properties

of (PEOPMMA)LiCF3 SO3 x wt% PEG electrolyte lms prepared
through SC and USMW methods were reported. It was revealed
that the dielectric parameters of these solid polymeric electrolyte
lms change signicantly with the sample preparation methods
and the PEG concentration. The ionic conductivity of unplasticized
electrolyte lm prepared through USMW method is two times
high as compared to that of the SC method prepared electrolyte

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

lm. It is found that the ionic conductivity of these electrolytes has

correlation with the dielectric strength and the polymer chain segmental motion relaxation time. This study conrms that the ions
mobility is due to cations coordinated polymer chain segmental
motion and their transportations occur by hopping mechanism.
The values of ionic conductivity and relaxation time activation
energies of these electrolytes are found in the range 0.220.33 eV.
The VTF behaviour of temperature dependence of the relaxation
time and conductivity conrms the coupling between the ions
mobility and polymer segmental dynamics in the polymer blend
electrolytes. These PEOPMMA blend based electrolytes have about
one to two orders of magnitude higher ionic conductivity at room
temperature as compared to the PEO and PMMA based electrolytes.
This signicantly enhanced conductivity at room temperature conrms the suitability of the PEOPMMA blend based electrolytes
for the lithium ion batteries and other electrochromic devices. The
unplasticized PEOPMMA blend electrolytes structures are found
amorphous due to blend miscibility and its complexations with the
lithium cations. But the amorphous phase gradually reduces as the
PEG concentration increases in the electrolytes, which is owing to
the same backbone units of PEG and PEO molecules.
Acknowledgements
Authors are grateful to the Department of Science and Technology (DST), New Delhi for providing the experimental facilities
through research projects Nos. SR/S2/CMP-09/2002, SR/S2/CMP0072/2010 and the DSTFIST program. One of the authors SC is
thankful to the DST, New Delhi for the award of SERB Fast Track
Young Scientist research project No. SR/FTP/PS-013/2012.
References
[1] Y. Kumar, S.A. Hashmi, G.P. Pandey, Ionic liquid mediated magnesium ion conduction in poly(ethylene oxide) based polymer electrolyte, Electrochim. Acta
56 (2011) 38643873.
[2] N. Chilaka, S. Ghosh, Dielectric studies of poly(ethylene glycol)/poly(methyl
methacrylate)/montmorillonite composite, Electrochim. Acta 134 (2014)
232241.
[3] R.J. Sengwa, S. Choudhary, Dielectric properties and uctuating relaxation
processes of poly(methyl methacrylate) based polymeric nanocomposite electrolytes, J. Phys. Chem. Solids 75 (2014) 765774.
[4] M. Ulaganathan, C.M. Mathew, S. Rajendran, Highly porous lithium-ion
conducting solvent-free poly(vinylidene uoride-co-hexauoropropylene)/
poly(ethyl methacrylate) based polymer blend electrolytes for Li battery applications, Electrochim. Acta 93 (2013) 230235.
[5] P. Aranda, Y. Mosqueda, E. Prez-Cappe, E. Ruiz-Hitzky, Electrical characterization of poly(ethylene oxide)clay nanocomposites prepared by microwave
irradiation, J. Polym. Sci. Part B: Polym. Phys. 41 (2003) 32493263.
[6] R.C. Agrawal, G.P. Pandey, Solid polymer electrolytes: material designing and
all-solid-state battery applications: an overview, J. Phys. D: Appl. Phys. 41
(2008) 223001.
[7] A. Karmakar, A. Ghosh, A comparison of ion transport in different polyethylene
oxidelithium salt composite electrolytes, J. Appl. Phys. 107 (2010), 104113(16).
[8] S.R. Mohapatra, A.K. Thakur, R.N.P. Choudhary, Effect of nanoscopic connement on improvement in ion conduction and stability properties of an
intercalated polymer nanocomposite electrolyte for energy storage applications, J. Power Sources 191 (2009) 601613.
[9] R.J. Sengwa, S. Sankhla, S. Choudhary, Effect of melt compounding temperature
on dielectric relaxation and ionic conduction in PEONaClO4 MMT nanocomposite electrolytes, Ionics 16 (2010) 697707.
[10] S. Choudhary, R.J. Sengwa, Dielectric spectroscopy and conrmation of
ion conduction mechanism in direct melt compounded hotpress polymer
nanocomposite electrolytes, Ionics 17 (2011) 811819.
[11] S. Choudhary, R.J. Sengwa, Effects of different anions of lithium salt and MMT
nanoller on ion conduction in melt compounded PEOLiXMMT electrolytes,
Ionics 18 (2012) 379384.

[12] J. Syzdek, M. Armand, M. Marcinek, A. Zalewska, G. Zukowska,

W. Wieczorek,
Detailed studies on the llers modication and their inuence on composite,
poly(oxyethylene)based polymeric electrolytes, Electrochim. Acta 55 (2010)
13141322.
[13] Y. Kumar, S.A. Hashmi, G.P. Pandey, Lithium ion transport and ionpolymer
interaction in PEO based polymer electrolyte plasticized with ionic liquid, Solid
State Ionics 201 (2011) 7380.

369

[14] B. Scrosati, J. Garche, Lithium batteries: Status, prospects and future, J. Power
Sources 195 (2010) 24192430.
[15] S. Choudhary, R.J. Sengwa, Effects of preparation methods on structure, ionic
conductivity and dielectric relaxation of solid polymeric electrolytes, Mater.
Chem. Phys. 142 (2013) 172181.
[16] T.K.J. Kster, L.V. Wullen, Cationanion coordination, ion mobility and the effect
of Al2 O3 addition in PEO based polymer electrolytes, Solid State Ionics 181
(2010) 489495.
[17] R.J. Sengwa, S. Choudhary, Dielectric relaxation spectroscopy and Xray diffraction studies of poly(ethylene oxide)lithium perchlorate electrolytes, Indian J.
Phys. 88 (2014) 461470.
[18] A.K. Nath, A. Kumar, Scaling of AC conductivity, electrochemical and thermal
properties of ionic liquid based polymer nanocomposite electrolytes, Electrochimica Acta 129 (2014) 177186.
[19] Y. Wang, B. Li, J. Ji, W.H. Zhong, Controlled Li+ conduction pathway to achieve
enhanced ionic conductivity in polymer electrolytes, J. Power Sources 247
(2014) 452459.
[20] S. Choudhary, A. Bald, R.J. Sengwa, Dielectric behaviour, ionic conductivity and
structure of high energy ball mill blended melt pressed and solution cast solid
polymeric nanocomposite electrolytes, Indian J. Pure Appl. Phys. 51 (2013)
769779.
[21] M. Deka, A. Kumar, Dielectric and conductivity studies of 90 MeV O7+ ion irradiated poly(ethylene oxide)/montmorillonite based ion conductor, J. Solid State
Electrochem. 17 (2013) 977986.
[22] H.W. Chen, F.C. Chang, The novel polymer electrolyte nanocomposite composed
of poly(ethylene oxide), lithium triate and mineral clay, Polymer 42 (2001)
97639769.
[23] S. Choudhary, R.J. Sengwa, Dielectric properties and structural conformation of
melt compounded PEOLiCF3 SO3 MMT nanocomposite electrolytes, Indian J.
Pure Appl. Phys. 49 (2011) 600605.
[24] H.M.J.C. Pitawala, M.A.K.L. Dissanayake, V.A. Seneviratne, B.E. Mellander, I.
Albinson, Effect of plasticizers (EC or PC) on the ionic conductivity and thermal
properties of the (PEO)9 LiTf: Al2 O3 nanocomposite polymer electrolyte system,
J. Solid State Electrochem. 12 (2008) 783789.
[25] N.K. Karan, D.K. Pradhan, R. Thomas, B. Natesan, R.S. Katiyar, Solid polymer electrolytes based on polyethylene oxide and lithium triuoromethane sulfonate
(PEOLiCF3 SO3 ): Ionic conductivity and dielectric relaxation, Solid State Ionics
179 (2008) 689696.
[26] X. Zhou, Y. Yin, Z. Wang, J. Zhou, H. Huang, A.N. Mansour, J.A. Zaykoski, J.J.
Fedderly, E. Balizer, Effect of hot pressing on the ionic conductivity of the
PEO/LiCF3 SO3 based electrolyte membranes, Solid State Ionics 196 (2011)
1824.
[27] M.R. Johan, O.H. Shy, S. Ibrahim, S.M.M. Yassin, T.Y. Hui, Effects of Al2 O3
nanoller and EC plasticizer on the ionic conductivity enhancement of
solid PEOLiCF3 SO3 solid polymer electrolyte, Solid State Ionics 196 (2011)
4147.
[28] R. Frech, S. Chintapalli, Effect of propylene carbonate as a plasticizer in high
molecular weight PEOLiCF3 SO3 electrolytes, Solid State Ionics 85 (1996)
6166.
[29] G.B. Appetecchi, F. Croce, J. Hassoun, B. Scrosati, M. Saloman, F. Cassel, Hot
pressed, dry, composite, PEObased electrolyte membranes I. Ionic conductivity characterization, J. Power Sources 114 (2003) 105112.
[30] M.R. Johan, L.B. Fen, Combined effect of CuO nanollers and DBP plasticizer on
ionic conductivity enhancement in the solid polymer electrolyte PEOLiCF3 SO3 ,
Ionics 16 (2010) 335338.
[31] P. Meneghetti, S. Qutubuddin, A. Webber, Synthesis of polymer gel electrolyte
with high molecular weight poly(methyl methacrylate)clay nanocomposite,
Electrochim. Acta 49 (2004) 49234931.
[32] N. Shukla, A.K. Thakur, Ion transport model in exfoliated and intercalated polymerclay nanocomposites, Solid State Ionics 181 (2010)
921932.
[33] M. Deka, A. Kumar, Enhanced electrical and electrochemical properties of
PMMAclay nanocomposite gel polymer electrolytes, Electrochim. Acta 55
(2010) 18361842.
[34] S. Ramesh, K.C. Wong, Conductivity, dielectric behaviour and thermal stability studies of lithum ion dissociation in poly(methyl methacrylate)based gel
polymer electrolytes, Ionics 15 (2009) 249254.
[35] S. Ahmad, T.K. Saxena, S. Ahmad, S.A. Agnihotry, The effect of nanosized TiO2
addition on poly(methylmethacrylate) based polymer electrolytes, J. Power
Sources 159 (2006) 205209.
[36] A.M.M. Ali, M.Z.A. Yahya, H. Bahron, R.H.Y. Subban, M.K. Harun, I. Atan,
Impedance studies on plasticized PMMALiX [X: CF3 SO 3 , N(CF3 SO2 )2 ] polymer electrolytes, Mater. Lett. 61 (2007) 20262029.
[37] S. Ramesh, L.C. Wen, Investigation on the effects of addition of SiO2 nanoparticles on ionic conductivity, FTIR, and thermal properties of nanocomposite
PMMALiCF3 SO3 SiO2 , Ionics 16 (2010) 255262.
[38] S. Rajendran, O. Mahendran, R. Kannan, Ionic conductivity studies in composite,
solid polymer electrolytes based on methylmethacrylate, J. Phys. Chem. Solids
63 (2002) 303307.
[39] S. Rajendran, R. Kannan, O. Mahendran, Ionic conductivity studies in
poly(methyl methacrylate)polyethylene oxide hybrid polymer electrolytes
with lithium salt, J. Power Sources 96 (2001) 406410.
[40] S. Rajendran, O. Mahendran, R. Kannan, Investigations on poly(methyl
methacrylate)poly(ethylene oxide) hybrid polymer electrolytes with dioctyl
phthalate, dimethyl phthalate and diethyl phthalate as plasticizers, J. Solid State
Electrochem. 6 (2002) 560564.

370

R.J. Sengwa et al. / Electrochimica Acta 142 (2014) 359370

[41] D. Shanmukaraj, G.X. Wang, R. Murugan, H.K. Liu, Ionic conductivity and
electrochemical stability of poly(methyl methacrylate)poly(ethylene oxide)
blendcermimc llers composites, J. Phys. Chem. Solids 69 (2008) 243248.
[42] S.M. Tan, M.R. Johan, Effects on MnO2 nanoparticles on the conductivity of
PMMAPEOLiClO4 EC polymer electrolytes, Ionics 17 (2011) 485490.
[43] K. Jeddi, N.T. Qazvini, S.H. Jafari, H.A. Khonakdar, Enhanced ionic conductivity
in PEO/PMMA glassy miscible blends: Role of nanoconnement of minority
component chains, J. Polym. Sci. Part B: Polym. Phys. 48 (2010) 20652071.
[44] K. Jeddi, N.T. Qazvini, S.H. Jafari, H.A. Khonakdar, J. Sey, U. Reuter, Investigating the effect of nanolayered silicates on blend segmental dynamics and
minor component relaxation behavior in poly(ethylene oxide)/poly(methyl
methacrylate) miscible blends, J. Polym. Sci. Part B: Polym. Phys. 49 (2011)
318326.
[45] M. Ghelichi, N.T. Qazvini, S.A. Jafari, H.A. Khonakdar, Y. Farajollahi, C. Schefer,
Conformational, thermal and ionic conductivity behavior of PEO in PEO/PMMA
miscible blend: Investigating the effect of lithium salt, J. Appl. Polym. Sci. 129
(2013) 18681874.
[46] P. Sharma, D.K. Kanchan, A comparison of effect of PEG and EC plasticizers on
relaxation dynamics of PEOPMMAAgNO3 polymer blends, Ionics 19 (2013)
12851290.
[47] P. Sharma, D.K. Kanchan, N. Gondaliya, M. Pant, M.S. Jayswal, Conductivity
relaxation in Ag+ ion conducting PEOPMMAPEG polymer blends, Ionics 19
(2013) 301307.

[48] P. Sharma, D.K. Kanchan, Effect of nanoller concentration on conductivity

and dielectric properties of poly(ethylene oxide)poly(methyl methacrylate)
polymer electrolytes, Polym. Int. 63 (2014) 290295.
[49] S. Choudhary, R.J. Sengwa, Intercalated clay structures and amorphous
behaviour of solution cast and melt pressed poly(ethylene oxide)clay
nanocomposites, J. Appl. Polym. Sci. 131 (2014) 39898.
[50] D. Saikia, A. Kumar, Ionic tansport in P(VDFHFP)PMMALiCF3 SO3
(PC + DEC)SiO2 composite gel polymer electrolytes, Eur. Polym. J. 41 (2005)
563568.
[51] R.J. Sengwa, K. Kaur, R. Choudhary, Dielectric properties of low molecular
weight poly(ethylene glycol)s, Polym. Int. 49 (2000) 599608.
[52] J.C. Dyre, T.B. Schrder, Universality of ac conduction in disordered solids, Rev.
Mod. Phys. 72 (2000) 873892.
[53] A. Karmakar, A. Ghosh, Dielectric permittivity and electric modulus of polyethylene oxide (PEO)LiClO4 composite electrolytes, Curr. Appl. Phys. 12 (2012)
539543.
[54] A. Ghosh, A. Pan, Scaling of the Conductivity Spectra in Ionic Glasses: Dependence on the Structure, Phys. Rev. Lett. 84 (2000) 21882190.
[55] A.K. Jonscher, Dielectric Relaxation in Solids, Chelsea Dielectric Press, London,
1983.
[56] D.K. Pradhan, R.N.P. Choudhary, B.K. Samantaray, Studies of dielectric and electrical properties of plasticized polymer nanocomposite electrolytes, Mater.
Chem. Phys. 115 (2009) 557561.