Int. J. Electrochem. Sci.

, 2 (2007) 861 - 871

InternatIonaI JournaI oI
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org


Effect of Plasticizer on Structural and Electrical Properties of
Polymer Nanocompsoite Electrolytes

Dillip K. Pradhan
1
, R. N. P.Choudhary
1,*
, B. K. Samantaray
1
, N. K. Karan
2
and R. S. Katiyar
2

1
Department of Physics And Meteorology, Indian Institute of Technology, Kahargapur-721302-India
2
Department of Physics, University of Puerto Rico, San Juan, PR 00931 USA
*
E-mail: [email protected]

Received: 27 August 2007 / Accepted: 7 September 2007 / Online published: 5 October 2007


Plasticized polymer nanocomposite electrolytes (PPNCEs) based on Poly (ethylene oxide) + NaI with
dodecyl amine modified montmorillonite (DMMT) as the filler and Poly (ethylene glycol) as the
plasticizer were prepared by a self-designed tape caster. The effect of plasticization on structural,
microstructure, thermal and electrical properties of the PPNCEs were investigated. The changes in the
structural and microstructural properties of the materials were investigated by XRD and SEM
techniques. Differential scanning calorimetry (DSC) technique was used to study the thermal
parameters (i.e., glass transition temperature (T
g
) and crystalline melting temperature (T
m
)) of the
nancomposites. Complex impedance analysis was used to calculate the bulk resistance of the
composites. The typical complex impedance spectrum of the samples comprises of a compressed
semicircle in the high frequency region (due to the bulk properties) followed by a tail (spike) in the
lower frequency region indicating the double layer response at the electrode/sample interface. The
maximum conductivity of PPNCE was found to be 1.05x10
-6
for x=50% of plasticizer (at 40
0
C). The
effect of plasticizer on the structural and physical properties of polymer nanocomposites was well
correlated.


Keywords: Polymer nanocomposite electrolyte; Plasticization, Complex impedance spectroscopy;
XRD; Electrical conductivity


1. INTRODUCTION
The polymer electrolytes (polymer-salt complexs) are important for both fundamental
understanding of fast ion transport in polymer electrolyte and their potential technological applications
in various electrochemical devices [1-6]. The pioneering work of Wright and co-workers [7, 8]
motivated researchers to work on solid polymer electrolytes. Later Armand et al. [9] explored the
possible applications of these materials for electrochemical devices. As it is well known, solid polymer
Int. J. Electrochem. Sci., Vol. 2, 2007

862
electrolytes (SPEs) have several advantages over the liquid counterpart such as desirable shape
mouldability, free from leakage, mechanical strength and flexibility of design, thereby permitting
miniaturization. Unfortunately, SPEs have the inherent problem of low ionic conductivity at ambient
temperature that acts as a barrier to their utility when compared with the existing conventional
liquid/hybrid electrolytes. The ionic conductivity of SPEs are strongly affected by various factors such
as (i) crystallinity of the material, (ii) simultaneous cation and anion motions and (iii) the ion-pair
formation (anion complex-cation interaction) [10, 11]. These factors reduce the cationic conductivity,
and therefore this act as a barrier for potential applications. To overcome these problems, the
realization of single ion conduction is fascinating alternative. Recently, an innovative approach was
made to use layered silicate clay (such as montmorillonite, hecrorite, laponoite etc.) based
nanocomposite to obtain the mobility of ions in polymeric matrix in a controlled way resulting in
single ion conducting polymer nanocomposite electrolytes (PNCEs) [12]. The clay layered silicate
nanocomposite could directly affect mobility of cation while reducing the mobility of anion to a
negligible limit due to the intercalation of cations into the layered silicate where bulky anion cannot
enter into that. This idea has attracted researchers to work on PNCEs to suppress dual ionic motions
and ion-pair formation [10, 12]. Some times, it is necessary for organic modification of the clay layers,
which makes the hydrophilic surface of montmorillonite (DMMT) as a hydrophobic. The hydrophobic
organic modifier facilitates the intercalation of hydrophobic polymer into MMT by reducing the
surface energy [13].
Berthier et al. [14] established that the ionic conductivity in polymer electrolytes is related to
the amorphous phase of the sample. One of the most successful approaches is to increase the
amorphous nature (i.e., reduction of polymer crystallinity) and hence ionic conductivity of SPEs by
incorporating suitable plasicizer into the polymer electrolyte. The essence of plasticization is to
enhance the conductivity of solid polymer electrolytes using low molecular weight and high dielectric
constant additives such as propylene carbonate (PC), ethylene carbonate (EC), polyethylene glycol
(PEG) etc. [15, 16]. These additives, increase the amorphous content of the polymer matrix and tend
to dissociate ion-pairs into free cations and anions thereby leading to an overall enhancement in
conductivity. However, to the best our knowledge, only a very few reports are available in the
literature which discuss the combined effect of the filler and the plasticizer on polymer salt complex
[17-21]. In view of the above, we have studied the effect of plasticization on the
microstructural/structural, thermal and electrical properties of the polymer nanocomposite electrolytes
based on poly (ethylene oxide)-NaI system dispersed with dodecyl amine modified montmorillonite
(DMMT) as filler and plasticized with polyethylene glycol (PEG
200
).


2. EXPERIMENTAL PART
2.1. Materials Preparation
Plasticized polymer nanocomposite electrolyte (PPNCE) films were prepared using a self-
designed tape caster. The commercially available Polyethylene oxide (PEO) (M/S Aldrich, M. W.~
6x10
5
), NaI (M/S Merck India Ltd, Mumbai India) and dodecyl amine modified Na
+
-montmorillonite
Int. J. Electrochem. Sci., Vol. 2, 2007

863
(DMMT) and poly ethylene glycol (PEG) (M/S Aldrich, M. W. = 200) were used for preparation of
PPNCEs. The details procedure for modification of montmorillonite is reported elsewhere [22]. An
appropriate ratio of PEO and NaI was dissolved in dehydrated acetonitrile, and the mixed solution was
stirred thoroughly for 12 h to allow polymer-salt complexation. Previously optimized ratio (5 wt %)
[23] of the ceramic filler DMMT was then added to the complex solution and further stirred for 12 h.
Finally, different concentrations of the plasticizer by wt. (wt.% of PEG in relation to PEO) were added
followed by continuous stirring for 12 h. Then it was casted using a self-designed tape caster of
desirable thickness and allowed to dry slowly at room temperature followed by vacuum drying. At the
end, the films were heated at ~40
0
C for 3-4 h to remove residual solvents, if any so as to get
freestanding thin films of the PPNCEs. The entire operation was carried out in an inert atmosphere
inside a glove box. The sample composition may be represented as: (PEO)
25
-NaI+5wt.% DMMT

+ x
wt.% PEG (x = 0, 5, 10, 20, 30, 40 and 50).

2.2. Materials Characterization
The x-ray diffraction (XRD) pattern of the PNCEs films was recorded at room temperature
using an x-ray powder diffractometer (Rigaku Miniflex) with CuK

radiation (=1.5405A
0
) in a wide
range of 2 (Bragg angles) (2
0
2 30
0
) at a scan speed of 0.5
0
minute
-1
. The surface morphology of
the plasticized composite polymer electrolytes (PCPEs) were obtained using a computer-controlled
scanning electron microscope; SEM, (JOELJSM, model 5800F). The film surfaces were gold coated
prior to being scanned under high-resolution field emission gun scanning electron microscope.
Thermal analysis was carried out using differential scanning calorimeter (Shimadzu, DSC-50) with a
low temperature measuring head and liquid nitrogen as coolant. About 10 mg of samples were crimped
in alumina pans inside the glove box (under argon atmosphere) and transferred to DSC cell for
measurement. The samples in alumina pans were stabilized by slow cooling to 100
0
C and then
heated to 150
0
C at 10
0
C/minute. Al
2
O
3
powder was used as reference material. The impedance data
were collected using a computer-controlled impedance analyzer (HIOKI LCR Hi TESTER Model:
3532) in the frequency range of 100 Hz to 1MHz. The impedance spectra/data of the cell SS | PCPE |
SS, (SS stands for stainless steel), were recorded using an input signal of amplitude 100mV at different
temperatures (room temperature to 150
0
C). The impedance spectrum was used to evaluate the bulk d.
c. conductivity and other related parameters of PPNCEs.


3. RESULTS AND DISCUSSION
The x-ray diffraction (XRD) pattern of plasticized polymer nanocomposite electrolyte
(PPNCE) films with different concentrations of PEG are compared in Fig. 1. The XRD patterns
comprise of characteristic peaks of DMMT at ~5
0
, polymer (PEO) at 2 ~ 19
0
and 23
0
and broad hump
at peak position of PEO for PPNCE films with different plasticizer concentration. The distance
between the clay sheets is given by the d
001
reflection of DMMT. The d
001
values for different
plasticizer concentration is close to 17.5 (for 2~5
0
) compared to 12 found for host silicate
(hydrated sample containing a monolayer of H
2
O). These pattern, therefore, suggest the formation of
Int. J. Electrochem. Sci., Vol. 2, 2007

864
nanocmposite, where polymer-salt complex have been intercalated between the nanometric gallery of
the montmorillonite. It is observed that the addition of plasticizer brings substantial changes in XRD
pattern of PPNCEs films. The shift in (001) peak position of MMT towards the lower with increase in
intensity was observed with increase in plasticizer concentration. This indicates the increase in the
gallery height of montmorillonite suggesting intercalation of more polymer salt complex. Also, the
characteristic peaks of PEO shifts towards the lower angle side with significant broadening on addition


Figure 1. Comparison of XRD patterns of (PEO)
25
NaI+ 5 wt % DMMT + x wt% of PEG
200
, with
different concentration of PEG (x).

Table 1. Some parameters calculated form XRD data of (PEO)
25
NaI+ 5 wt % DMMT + x wt% of
PEG
200
, with different PEG concentration.










of plasticizer. This shift towards the lower angle side indicates an increase in interplaner spacing of the
(100) plane. It is possibly due to the incorporation of the small plasticizer molecule in to the
interplaner spacing of the matrix, but for (010) plane it remains nearly constant. The structural
MMT (001) Peak PEO Peak (100) PEG
Concentration
d
001

()
L
(nm)
d
100
()
L
(nm)
0% 16.92 12.3 4.58 42
10% 17.23 12.51 4.61 42.6
20% 17.38 10.1 4.6 42.1
30% 17.35 17.9 4.61 40.7
40% 17.38 19.5 4.60 33.6
50% 17.04 11.8 4.61 40.8
5 10 15 20 25 30
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
* PEO Peak
0

1

0

*
1

0

0

*
0

0

1
x= 5 %
x = 10 %
x= 20 %
x= 30 %
x= 40 %
x= 50 %
x = 0 %
I
n
t
e
n
s
i
t
y

(
a
.

u
.
)
Bragg Angle (2)
Int. J. Electrochem. Sci., Vol. 2, 2007

865
parameters calculated for (001) and main PEO (1 0 0) peak are given in Table-1. Comparison of the
crystallite size (L) calculated from Scherres equation for 100 peak of PEO for different concentration
of plasticizer exhibits that the crystallite size decreases on increasing plasticizer concentration. These
observations suggest an enhancement in the degree of disorder and amorphocity in the polymeric films
on plasticization [19].

Figure 2. SEM micrographs of PPNCEs thin films of (PEO)
25
-NaI+5wt.% DMMT

+ x wt.% PEG
200
with
different concentration of x.(i.e., (a) x= 0, (b) x=10, (c) x=20, and (e) x = 50)).

Fig. 2 shows scanning electron micrographs of PPNCE films (PEO
25
-NaI+5 wt % DMMT+x
wt% PEG) for different value of x. Comparison of the surface morphology of PPNCEs show a marked
change in the surface properties and texture of the nanocomposite polymeric thin films on addition of
plasticizer. On addition of plasticizer, it is observed that there is a decrease in the spherulite size and
for higher concentration, it no longer exist. The surface roughening and crystalline texture appear to be
decreases gradually, which results into the appearance of smooth texture of the surface on increasing
plasticizer concentration. These changes may be attributed to the effect of plasticization resulting in the
reduction of crystallinity of host polymer (i.e., polyethylene oxide) and subsequent enhancement in the
overall amorphous fraction in the material [24].
Fig.3 shows the DSC traces of (PEO)
25
NaI+ 5 wt % DMMT + x wt% of PEG
200
, with
different value of x in the temperature range of 100
0
C to 0
0
C (A)and 0 to 150
0
C (B) respectively.
The DSC pattern shows a step change (Fig. 3 (A)) attributed to glass transition temperature (T
g
) of the
PNCEs. The step change in DSC curve is followed by a predominant endothermic peak (T
m
) (Fig. 3
(B)) appearing in the temperature range of 50-60
0
C. The endothermic peak is due to the melting of
(a) (b)
(c)
(d)
Int. J. Electrochem. Sci., Vol. 2, 2007

866
crystalline PEO. The thermal parameters (T
g
and T
m
) calculated from the DSC curves are tabulated in
Table-2. The glass transition temperature was obtained at the mid point of the step changes of curve
and the melting temperature was determined at the peak temperature of the melting endotherm. It is
observed that both T
g
and T
m
decrease on plasticizer addition. The addition of plasticizer helps in
increasing the local chain flexibility by lowering the T
g
. As we know, the increase in chain flexibility
is a measure of the ability of a chain to rotate about the chain bonds. A decrease in the value of T
g

helps in easy movement of the polymer chains as a result an increase in the conductivity is expected
[15].
(A) (B)

Figure 3. (A) Variation of DSC pattern in the temperature range 105
0
C to 0
0
C with different
concentration (x) of PEG (a) x = 0%, (b) x = 10%, (c) x = 20% (d) x = 30% and (e) x = 50%. (B)
Variation of DSC pattern in the temperature range 0
0
C to 150
0
C with different concentration (x) of
PEG (a) x = 0%, (b) x = 10%, (c) x = 20%, (d) x = 30% and (e) x = 50%.

Table 2. Comparion of T
g
(
0
C) and T
m

(
0
C) polymer nanocomposite thin films for different value of x.

PEG concentation
(x)

T
g
(
0
C)


T
m

(
0
C) Peak
0 -32.17 57.36
5 -37.75 58.20
10 -51.68 56.63
20 -67.93 55.14
30 -69.54 54.91
50 -76.90 54.04

Fig. 4 represents the complex impedance spectrum of PPNCE films (PEO)
25
-NaI+5wt.%
DMMT

+ xwt.%PEG
200
(x = 0, 5, 10, 20, 30 and 40) for various concentrations of PEG
200
. The
impedance spectrum comprises of a distorted semicircular arc in the high frequency region followed
by a spike in the lower frequency region. The high frequency semicircle is due to the bulk properties
0 20 40 60 80 100 120 140
-8
-6
-4
-2
0
2
4
6
8
10
12
14
16
18
20
(e) x = 50 %
(d) x = 30 %
(c) x = 20 %
(b) x = 10 %
(a) x = 0 %
H
e
a
t

F
l
o
w

(
e
n
d
o
)
Temperature (
0
C)
Int. J. Electrochem. Sci., Vol. 2, 2007

867
and the low frequency spike is due to the material and electrode interface properties of the
nanocomposites. The intercept of the semicircle with the real axis (Z') in the low frequencies region
gives rise to the bulk (ionic) resistance (R
b
) of the materials [1]. Generally, equivalent circuit is used
for the analysis of impedance spectroscopy because it is simple and can provide the complete picture
of the system. [25]. The flattening/broadening of semicircle and the tilting of the spike can only be
explained by incorporating a constant phase element (CPE) in equivalent circuit (Fig.4). This CPE
replacing the capacitors in the circuit is nothing, but a leaky capacitor, which has an intermediate
characteristic between a resistor and a capacitor [26, 27]. The analysis and fitting of the impedance
data according to the equivalent circuit (as shown in Figure) can be accomplished by a commercially
available computer software Z SimpWin [28]. The solid line (representing fitting of the experimental
data) shows that there is good agreement between the experimental data and the proposed equivalent
circuit. The bulk resistance is obtained on fitting the experimental data using the equivalent circuit by
the software. It is found that the bulk resistance decreases with increase in plasticizer concentration.

Figure 4. Complex impedance spectrum of (PEO)
25
-NaI+5wt.% DMMT

+ xwt.%PEG
200
(x = 0, 5, 10,
20, 30, 40 and 50). The solid line represents the fitting of the experimental data in accordance with the
equivalent circuit.

The value of
dc
of the plasticized composite polymer electrolyte was evaluated from complex
impedance spectra and expressed as a function of plasticizer concentration at 40
0
C. It is observed that
the
dc
increases monotonically with increase in PEG concentration (Fig. 5). The maximum
conductivity was found to be 1.05x10
-6
for x=50% plasticizer. An enhancement in conductivity by one
0 10 20 30 40 50 60
0
10
20
30
40
50
60
-
Z
"

(
k

)
Z' (k)
x=0 % PEG
x=10 % PEG
x=20 % PEG
___________ Fit
0 5 10 15 20
0
5
10
15
20
-
Z
"

(
k

)
Z' (k)
x=30 % PEG
x=40 % PEG
x=50 % PEG
_____________ Fit

Int. J. Electrochem. Sci., Vol. 2, 2007

868
order of magnitude is observed on plasticiztaion when compared to that of the nanocomposite
(plasticizer free, x=0%) polymer electrolyte films has been observed.

Figure 5. Variation of d. c. conductivity (40
0
C) as a function of plasticizer concentration

Figure 6.Variation of d. c. conductivity as a function of temperature with different concentration (x) of
PEG (a) x = 0%, (b) x = 10% (c) x = 20%, (d) x = 30% and (d) x = 50%.

Fig. 6 shows the variation of d. c. conductivity of PPNCEs as a function of temperature (log
vs 10
3
/T) for different concentration of PEG. The variation of conductivity indicates that the
conductivity increases with rise in temperature. The temperature dependence of conductivity of
electrolyte films exhibit a typical VTF (Vogel-Tamman-Fulcher) behaviour as expressed by an
empirical relation:


] [
] [
exp
0
0
T T k
E
a

(i)
0 10 20 30 40 50
1E-7
1E-6

d
c

(
S
c
m
-
1
)
PEG Concentration
40
0
C
2.4 2.6 2.8 3.0 3.2 3.4
1E-7
1E-6
1E-5
1E-4
1E-3
2.4 2.6 2.8 3.0 3.2
1E-8
1E-7
1E-6
1E-5
1E-4
1E-3

d
c

(
S
C
m
-
1
)
10
3
/T (K
-1
)
(a) x = 0 % PEG

d
c

(
S
C
m
-
1
)
10
3
/T (K
-1
)
(b) 10 % PEG
(c) 20 % PEG
(d) 30 % PEG
(e) 40 % PEG
(f) 50 % PEG
Int. J. Electrochem. Sci., Vol. 2, 2007

869
where
0
is the pre exponential factor, k

= Boltzmann constant, E
a
is the activation energy and T
0
is a
reference temperature identified as the equilibrium glass transition temperature which is usually 50K
lower than that of the glass transition temperature (T
g
).
Fig. 7 shows the variation of glass transition temperature (T
g
), crystalline melting temperature
(T
m
) as a function of plasticizer concentration. The variation of T
g
and T
m
has been correlated with the
electrical conductivity for different concentration of plasticizer. Addition of plasticizer decreases the
value of T
g
and T
m
and increase the conductivity of the materials. It is believed that plasticizers are
basically low molecular weight organic solvents (mostly liquid), added to a polymer matrix to modify
its physical properties such as flexibility (by lowering the glass transition temperature), microstructure,
viscosity/internal friction etc. Further, plasticizer molecules are relatively small in size as compared to
that of polymer host molecule, and hence can easily penetrate into the polymer matrix, causing an
interaction between plasticizer molecule and polymer chain molecules. This may reduce the cohesive
forces operating between the polymer chains resulting in an increase in the chain segmental mobility.
The overall result is an increase in the conductivity of polymer nanocomposite electrolyte on the
addition of plasticizers [19, 29].
Figure 7. Effect of PEG concentration on (a) d. c. conductivity, (b) glass transition temperature (T
g
)
and (c) malting temperature (T
m
) of PPNCEs system of (PEO)
25
-NaI+5 wt.% DMMT+ x wt.% PEG

4. CONCLUSIONS
A group of plasticized polymer nanocomposite electrolytes having heterogeneous combination
(polymer-salt-filler-plasticizer) was prepared and characterized. The effect of plasticization on
0 10 20 30 40 50
10
-8
10
-7
10
-6
(a)

d
c

(
S
c
m
-
1
)
PEG Concentration
0 10 20 30 40 50
-80
-70
-60
-50
-40
-30
(b)

T
g

(
0
C
)
0 10 20 30 40 50
54
56
58
(c)
T
m

(
0
C
)

Int. J. Electrochem. Sci., Vol. 2, 2007

870
electrical conductivity and other physical properties was also investigated. The change in the surface
morphology and increase in the amorphous content on addition of plasticizer were observed. Both T
g

and T
m
of PPNCEs were found to be decreased on increasing plasticizer concentration. The electrical
conductivity was studied using a. c. impedance spectroscopy was found to be dependent on plasticizer
concentration. A substantial enhancement in the electrical conductivity, by one order of magnitude of
the PPNCEs was observed as compared to polymer nanocomposite electrolyte (x=0% PEG) films
without any plasticizer. This enhancement in electrical conductivity of the PCPE films agrees well
with the changes in the local microstructure/structure on plasticizer addition. The temperature
dependence of conductivity behavior obeys VTF pattern.


ACKNOWLEDGEMENTS
We are thankful to Prof. S. K. Srivastava, Department of Chemistry, I. I. T. Kahargapur-721302-India
for some help in experimental work.


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