Material properties

Effect of nano TiO

2
ller on the structural and electrical
properties of PVP based polymer electrolyte lms
M. Ravi
a,
*
, K. Kiran Kumar
a, b
, V. Madhu Mohan
c
, V.V.R. Narasimha Rao
a
a
Sri Venkateswara University, Department of Physics, Tirupati 517 502, India
b
GITAM University, Department of Engineering Physics, GIT, Visakhapatnam 530 045, India
c
Shizuoka University, Research Institute of Electronics, Japan
a r t i c l e i n f o
Article history:
Received 13 October 2013
Accepted 3 December 2013
Keywords:
Nanocomposite polymer electrolytes
XRD
FT-IR
SEM
Ionic conductivity
Cationic transference numbers
a b s t r a c t
Acomposite polymer electrolyte systembasedonPVP:KIO
4
withdispersednanoTiO
2
ller in
different concentrations was prepared by solution casting. Structural investigations were
carried out using X-ray diffraction, Fourier transform infrared (FT-IR) spectroscopy and
scanning electronmicroscopy (SEM). Electrical conductivity measurements were performed
by a computer controlled phase sensitive multimeter (PSM 1700) in the frequency and
temperature range 1 Hz1 MHz and 303373 K, respectively. It was observed that the
magnitude of conductivity increased with increase in the nano TiO
2
ller concentration as
well as with temperature. The addition of nanoTiO
2
ller to the PVP:KIO
4
electrolyte system
was found to result in enhancement of the ionic conductivity. The maximum ionic conduc-
tivity 0.665 10
3
S/cm was obtained for 10 wt% nano TiO
2
ller in the composite at room
temperature. The conducting species of charge transport in these nano composite polymer
electrolyte lms were examinedby the Watanabe technique andit was foundthat the charge
transport is predominantlydue tocations. Using these polymer electrolytes (KIO
4
complexed
and TiO
2
nano composite), electrochemical cells were fabricated with the conguration of K/
(Polymer lm)/(I
2
C electrolyte), and discharge characteristics were studied under a
constant load of 100 kU. Various cell parameters, such as open circuit voltage, short circuit
current, power density and energy density were determined.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
In recent years, polymer inorganic salt complexes have
been widely studied as solid electrolytes because of their
potential importance in the development of solid state ionic
devices such as batteries, supercapacitors, electrochromic
display devices, etc. Despite 30 years of history of polymer
electrolytes used in ionic devices, some fundamental prob-
lems and questions are still unsolved. Among them, low
ionic conductivity, low cation transference numbers at
ambient temperature and the formation of resistive layers
on the electrode electrolyte interface are crucial. To
overcome these problems, various modications of polymer
salt complexes have been explored but the successes are
limited [1]. One of the most promising approaches is to
prepare composite polymer electrolytes. The composite
polymer electrolytes usually consist of three components:
polymer matrix, dopant salt and nano ller. The basic
method of composite polymer electrolyte formation is the
incorporation of nano ller particles into the polymer salt
matrix. The role of ller in a solid polymeric electrolyte
system is crucial as it serves as an agent to improve the
conductivity of the electrolyte. There are two types of llers
that can be introduced into the polymer electrolyte system,
namely, organic and inorganic molecular llers. The disad-
vantage of organic molecular llers such as propylene car-
bonate (PC) and ethylene carbonate (EC) is that they are
more expensive compared with inorganic molecular llers.
* Corresponding author.
E-mail addresses: m.raviphd@gmail.com, kokila.12345@gmail.com
(M. Ravi).
Contents lists available at ScienceDirect
Polymer Testing
j ournal homepage: www. el sevi er. com/ l ocat e/ pol yt est
0142-9418/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymertesting.2013.12.002
Polymer Testing 33 (2014) 152160
Most of the research efforts have, therefore, been directed
towards the improvement of the ambient temperature ionic
conductivity, while retaining the mechanical properties and
stability towards metallic anodes by the incorporation of
nano size inorganic llers such as Al
2
O
3
, SiO
2
, TiO
2
etc in the
polymer salt systems. These systems are generally knownas
nano composite polymer electrolytes (NCPEs). It has been
shown that nanosized ceramic ller particles incorporated
into the polymer salt matrix can act as solid plasticizers
inhibiting crystallization kinetics and promoting the
retention of the amorphous phase down to sub ambient
temperatures. These nano composite polymer electrolytes
have shown enhanced ionic conductivities and improved
mechanical and thermal stability. They also have better
electrochemical stability towards a metal anode and an
enhanced cation transport numbers.
The effects of dispersing insulating ceramic ller parti-
cles such as Al
2
O
3
, SiO
2
and TiO
2
on various physical/elec-
trolytic properties of NCPEs have been investigated by
various workers [24]. It has been observed, in general, that
the particle size and the physical nature of the dispersed
particles play a signicant role. Hence, dispersal of nano-
sized ceramic ller particles has been found to be more
effective in the NCPE systems, especially in terms of
improvement in mechanical, physical and electrochemical
properties. The enhancement in electrical conductivity due
to the addition of inert ller particles has been generally
explained in terms of the disruption of crystallization in the
polymer host matrix. The improvement in the mechanical
properties has been explained on the premise that the ller
particles act as a supporting matrix for the conducting
polymer electrolytes so as to retain an overall solid struc-
ture, even at higher temperatures. All these physical
properties, once optimised, would make them suitable
candidates for solid state ionic device applications.
Poly (vinyl pyrrolidone) (PVP) is a commercially avail-
able, inexpensive polymer, which is highly soluble in polar
solvents such as water, alcohol etc. PVP deserves a special
attention because of its good electrical properties, easy
processability and charge transport mechanism[5]. Further,
PVP is an amorphous polymer and possesses high T
g
due to
the presence of the rigid pyrrolidone group, which is known
to formvarious complexes with many inorganic salts [6]. In
previous studies, 15 wt% KIO
4
complexed PVP polymer
electrolyte exhibited optimum electrical properties [7].
Some research work was also reported on the effect of TiO
2
on the thermal, electrical properties of different polymer
electrolytes [810]. Inviewof above, inthepresent paper we
reported the effect of TiO
2
nanoparticles on the structural
and electrical properties of PVP:KIO
4
polymer lms.
2. Experimental
2.1. Materials
Poly (vinyl pyrrolidone) (PVP) fromAldrich Chemical Co.
Ltd. (USA), average molecular weight of 1,30,000 was used
as received. Potassiumperiodate salt (KIO
4
)(Extra pure) (SD
Fine-Chem Limited, India) was used as dopant, and triple
distilled water was used as common solvent for the prep-
aration of complexed polymer electrolytes.
2.2. Polymer lm preparation
Nano composite polymer electrolyte lms of thickness
w120 mm were prepared by a solution casting technique
[11]. In this process, the appropriate ratios of polyvinyl
pyrrolidone (PVP) and potassium periodate (KIO
4
) salts
wereinitially dissolvedintriple distilledwater andstirredat
room temperature for w10 hours to get a homogeneous
polymer salt solution. Thereafter, different weight % of nano
TiO
2
powder was added to PVP:KIO
4
polymer salt complex
system and stirred thoroughly for a further 1012 hours at
room temperature (w30

C) for complete dissolution.
Finally, viscous solutions were poured into poly propylene
dishes and allowed to evaporate slowly at room tempera-
ture to obtain free-standing nano composite polymer elec-
trolyte lms. The lms were dried at w40

C for 6 h to
remove any trace of the residual solvent in the electrolytes.
The harvested lms were stored in highly evacuated desic-
cators to avoid moisture absorption. The thickness of these
lms was determinedbya mechanical stylus methodusinga
German made Perthometer and was found to be approxi-
mately 120 mm. The accuracy is about 5 mm.
2.3. Structural investigations
The X-ray diffraction patterns of nano composite poly-
mer electrolyte lms were recorded using a SEIFERT, XRD
3003 TT, X-ray diffractometer with CuKa radiation
(l 1.540A

) and graphite monochromator at room tem-

perature. The diffraction patterns were recorded at the
Bragg angle (2q) in the range of 5

60

with a scan rate 5

per minute. FTIR absorption spectra of the lms were

recorded using Thermo Scientic Nicolet IR200 spectrom-
eter in the wave number range of 4004000 cm
1
. The FTIR
experiments were performed in a dynamic nitrogen at-
mosphere by averaging 16 scans per sample, keeping an
optical resolution of 4 cm
1
for all the spectra. The surface
morphology of the lms was observed by scanning electron
microscope (CARLZEUSS EVOMA 15, England) operated at
20 kV accelerating voltage. The samples were coated with a
thin layer of gold using a sputter coater, to minimize sample
charging effects due to the electron beam.
2.4. Electrical characterization
The complex impedance measurements were carried
out by using a computer controlled (Newton 4th Ltd, UK)
phase sensitive multimeter (PSM-1700) in the frequency
range 1 Hz1 MHz with a signal level of 20 mV. The sam-
ples were vacuum dried at 313K for 1 hour and,
M. Ravi et al. / Polymer Testing 33 (2014) 152160 153
subsequently, the measurements were recorded by sand-
wiching the electrolyte lm between two electrodes which
were assembled in a temperature controlled INDFURR
furnace. The bulk electrical conductivity of the different
nano composite polymer electrolytes was calculated from
the complex impedance plots. The temperature depen-
dence of ionic conductivity was measured by heating the
samples from 303K373K.
Cationic/Anionic transport numbers were evaluated
using the combination of complex impedance and a dc po-
larization measurement technique suggested by Watanabe
et al. [12]. In this technique, the nano composite polymer
samples were sandwiched between two potassium revers-
ible electrodes in the form of cell geometry K/electrolyte
sample/K. Potassiumforms a non- blocking electrode for K

ions while it is a blocking electrode for the anions. Electro-

chemical cells were fabricated with a conguration of
K(anode)/(Polymer lm)/(I
2
C electrolyte) (cathode).
3. Results and discussion
3.1. XRD analysis
X-ray diffraction studies are most useful for the deter-
mination of characteristics of the sample, such as crystal
structure, crystallite size and crystallinity. In the present
investigations, the X-ray diffraction method has been used
only in a limited perspective to identify the following.
1. Crystalline and amorphous nature of the material.
2. Relative amorphicity of the composite lms.
The X-ray diffraction patterns of PVP:KIO
4
, nano ceramic
powder TiO
2
and different compositions of TiO
2
nano-
ceramic ller dispersed nanocomposite polymer lms are
shown in Fig. 1. A comparative study of XRD patterns of
PVP:KIO
4
, nano ceramic powder and nanocomposite poly-
mer lms reveals the following.
The XRD prole of PVP:KIO
4
(85:15) shows a broad peak
between 2q w 10

15

which can be attributed to the

amorphous nature of the lm [13]. When nano ceramic
ller is added to PVP:KIO
4
complex, the intensity of broad
peak decreases and widens, which implies that the PVP
matrix augmented the amorphous domains. As the wt% of
TiO
2
nano ller increases, the intensity of the PVP diffrac-
tion peak weakens, suggesting that the interaction between
PVP chains and nano ller particles leads to decrease of
intermolecular interaction of PVP chains, thereby resulting
in increase of the amorphicity of PVP. This facilitates sig-
nicant motion of polymer chains in the amorphous phase.
The XRD patterns of TiO
2
nano ceramic powder show
intensive sharp peaks, which indicate its crystalline nature.
The observed peaks are well matched with the JCPDS card
no: 84-1750, which conrms TiO
2
is an orthorhombic sys-
tem. The average crystallite size of nano ceramic llers in
different compositions of composite electrolytes has been
calculated by the Scherrer formula [14], and found to be
17 nm. As the nano ller concentration increases, the peaks
corresponding to the nano ller become prominent. In the
composite, some of the crystalline peaks pertaining to TiO
2
are found to disappear and some peaks shifted indicates
the involvement of nano ceramic ller particles in dis-
rupting the structure. Persistence of crystalline peaks cor-
responding to nano ceramic ller in the composite polymer
lms suggests the presence of undissolved nano ller par-
ticles in the polymer matrix. These peaks are attributed to
nano TiO
2
particles as a separate phase [15]. Similar
behaviour was observed by other researchers [16,17].
3.2. FTIR analysis
FTIR spectroscopy is a powerful tool for characterizing
the detailed structure of polymer lms. Fig. 2 shows the
FTIR spectra of PVP:KIO
4
(85:15), nano TiO
2
powder and
nano composite polymer electrolytes dispersed with 4, 8
and 10 wt%. The following spectral features have been
observed on comparing the spectra of complexed PVP with
those of nanocomposite and TiO
2
ller.
The vibrational bands observed at 2998 cm
1
,
1721 cm
1
, 1391 cm
1
are ascribed to aliphatic CH
stretching, C]O stretching and CH bending vibrations,
respectively, and their band width decreases with the
addition of TiO
2
ller. Some new bands at 767 cm
1
,
495 cm
1
are observed and the 819 cm
1
band disappeared
with the addition of TiO
2
nano particles. These observed
spectral changes are indication of the complex formation.
The dispersed phase composite nature of the materials
has also been conformed from the FTIR studies. A com-
parison indicates that no distinct changes in the peak po-
sitions of the PVP complexes have been observed after
dispersing the nano TiO
2
ller particles. A low intensity
peak appeared at 750 cm
1
which is assigned to TiO
2
. This
also conrms the presence of nano TiO
2
in polymer com-
posites as separate phase. This separate phase of TiO
2
llers
Fig. 1. XRD patterns of composite polymer electrolyte lled with various
amount of TiO
2
nanoparticles and nano TiO
2
powder.
M. Ravi et al. / Polymer Testing 33 (2014) 152160 154
dispersed in polymer electrolyte lms has been observed in
SEM and XRD studies also, as discussed above.
3.3. SEM analysis
The compatibility between the polymer and the ceramic
llers has great inuence on the properties (thermal, me-
chanical and optical) of the polymer electrolytes. SEM is
often used to assess the compatibility between the various
phases through the detection of phase separations and
interfaces [11]. Although the size of the ceramic llers can
be at the nanoscale level, it is prudent to investigate
whether the ceramic llers remain as separate primary
particles, or are coagulated by the processes involved in the
fabrication of composite polymer electrolytes. There have
been few reports on the size and the morphology of the
particles after dispersal in polymer electrolytes.
The morphology of the polymer lms have been
observed using a CARL ZEISS EVO 25 scanning electron
microscope. The surface morphology could be modulated
by both ionic salt and nano ceramic ller particles [1316].
SEM micrographs of nano TiO
2
llers and different con-
centrations of nano TiO
2
ller dispersed nano composite
polymer electrolytes are shown in Fig. 3(a)(d). From the
gures, it is observed that surface morphology changes
considerably when nano TiO
2
ller is incorporated in the
complexed polymer matrix.
The surface morphology of the nano composite polymer
lms shows lumps of TiO
2
on the top surface. These lumps
possess crystalline structure embedded in the polymer
matrix. The presence of crystalline phase in the samples
has been observed in XRD patterns as sharp peaks which
are attributed to nano TiO
2
. The dark and smooth back
ground corresponds to the amorphous nature of the host
polymer.
The compatibility of the PVP matrix with nano particles
is uniform and homogenous when the TiO
2
content is less
than 10 wt%. When the nano ller content is more than
10 wt%, the composites showed a dispersion problem with
agglomeration of ller particles. The size of the nanoTiO
2
ller particles was examined from SEM images; these re-
sults were in good agreement with the results obtained
from XRD analysis.
3.4. Impedance analysis
Typical ac impedance spectra of 10 wt.% nano TiO
2
particles dispersed nanocomposite polymer electrolyte at
different temperatures are shown in Fig. 4, which demon-
strate normal impedance behavior such as a depressed
semicircular portion followed by a spike. The high fre-
quency semicircle arc is due to the parallel combination of
bulk resistance and bulk capacitance. The low frequency
response appears as an inclined spike, which is a charac-
teristic of blocking double layer capacitance (C
dl
) whose
magnitude can be estimated fromany position on the spike
using the equation:
Z
0

1
2pfC
dl
where f is the frequency and C
dl
is the capacitance at cor-
responding frequency f. Furthermore, the inclination of the
spike at an angle less than 90

to the real axis is due to the

roughness of the electrode electrolyte interface [18].
In Fig. 4, the lowfrequency end of the semicircle and the
high frequency end of the straight line coincide at the bulk
resistance of the nano composite polymer electrolyte
(NCPE) on the real axis [19]. It can be seen from Fig. 4 that
the magnitude of bulk resistance decreases with increase in
temperature. Ionic conductivity of the NCPE was calculated
from the measured bulk resistance (R
b
) and dimensions of
the nano composite polymer lm (i.e thickness and cross
section area) at ambient temperature and are presented in
Table 1. From Table 1, it can be noted that the ionic con-
ductivity of the NCPEs is improved by adding nano TiO
2
ller particles.
3.5. Concentration dependence of ionic conductivity
The ionic conductivity of a polymer electrolyte depends
on the concentration of the conducting species and their
mobility. The variation of ionic conductivity at room tem-
perature (303 K) as a function of nanoTiO
2
ller concen-
tration is shown in Fig. 5. The ionic conductivity increases
with increase of nano TiO
2
ller concentration until a
maximum (0.665 10
3
S/cm) is reached at 10 wt% TiO
2
.
The variation of bulk resistance at room temperature as a
function of nanoTiO
2
concentration is shown in the inset of
Fig. 5.
It is believed that the nano sized ceramic ller, due to its
large surface area, prevents local PVP chain reorganization
with the result of locking in at ambient temperature a high
degree of disorder characteristic of the amorphous phase,
Fig. 2. FTIR spectra of PVP:KIO
4
(85:15) and different concentration of TiO
2
dispersed composite polymer electrolytes.
M. Ravi et al. / Polymer Testing 33 (2014) 152160 155
which in turn favours high ionic transport [20]. However,
the conductivity enhancement in the composite polymer
electrolytes cannot be solely attributed to the retention of
the amorphous phase caused by the steric hindrance effect
of the nanometric ceramic ller. Therefore, the model must
be extended to consider other effects involving the ceramic
ller, such as Lewis acid-base interactions, in order to
explain the overall conductivity enhancement observed in
these nano-composite polymer electrolytes. In addition, to
stabilize the amorphous state of the polymer, the dispersed
ller may promote specic structural modications via
Lewis acid base reactions between their surface states and
the PVP segments. In particular, one may assume that the
Lewis acid groups of the ller could probably compete with
the Lewis acid K

cations for the formation of complexes

with the PVP chains, as well as with the anions of the added
KIO
4
salt. This in turn may result in local structural modi-
cations occurring at the ceramic ller surface, due to the
specic actions of the polar surface groups of the nano
ceramic ller which may act as:
1. Cross-linking centres for the PVP segments, thus
lowering the tendency to PVP reorganization and
promoting structural modication of the polymer
chains. The expected effect is the promotion of K

con-
ducting path ways at the ceramic surface, which nally
results in enhancement of the ionic conductivity.
2. Lewis acid-base interaction centres for the electrolyte
ionic species lowers ionic coupling, which is expected to
promote salt dissociation via a sort of ion-ceramic
complex formation and, nally, results an enhancement
of the K

ion transference number.

X-ray diffraction, FTIR, spectroscopy studies have sup-
ported this model in the present investigations. These re-
sults may be supported by K

transference number
measurements.
The conductivity is found to decrease after an optimum
concentration of 10 wt% TiO
2
is crossed. This is because of
the fact that, when the optimum concentration is attained,
further addition of ller results in build up of the agglom-
erated ller portion (a continuous non-conductive phase).
This agglomerated ller portion acts as an electrically inert
component which would block potassium ion transport,
resulting in an increase in total resistance of the composite
polymer electrolyte. Due to the ultrane nature of the nano
Fig. 3. (a)(d): SEM photographs of Nanocomposite polymer electrolytes.
M. Ravi et al. / Polymer Testing 33 (2014) 152160 156
ceramic ller particles, these small particles tend to form
large agglomerates [21].
3.6. Temperature dependent ionic conductivity
The temperature dependence of the ionic conductivity
of the NCPE was evaluated and log s vs 1000/T plots are
presented in Fig. 6 i.e. From the gure, it is observed that
the ionic conductivity increases with increase of tempera-
ture for all the nano composite polymer electrolytes. The
behaviour of conductivity enhancement can be understood
in terms of the free volume model [22]. As temperature
increases, the polymer can expand easily and produce free
volume. Thus, ions, solvated molecules or polymer seg-
ments can move into the free volume. The resulting con-
ductivity, represented by the overall mobility of ions and
the polymer, is determined by the free volume around the
polymer chains. Therefore, as temperature increases, the
free volume increases. This leads to an increase in ion
mobility and segmental mobility that will assist ion
transport.
Fig. 6 exhibits the ionic conductivity dependence of the
temperature ranging from 303373 K for nano composite
polymer electrolytes. The ionic conductivity of all
composite polymer electrolytes follows the Arrhenius
equation [23].
s s
0
exp E
a
=kT
where s
0
is the pre-exponential factor, E
a
is the activation
energy and k is the Boltzmann constant. The pre-
exponential term in the Arrhenius equation is related to
Fig. 5. Variation of ionic conductivity with nano TiO
2
concentration at room
temperature.
Fig. 6. Arrhenius plots for different concentrations of TiO
2
composite
polymer electrolytes.
Table 1
Roomtemperature ionic conductivity and transference numbers t
K
, t
IO

4
.
Sample Conductivity at 303K Transference numbers
Cationict
K
) Anonic (t
IO

0% TiO
2
1.42 10
4
0.366 0.624
4%TiO
2
5.02 10
4
0.552 0.441
8%TiO
2
5.74 10
4
0.584 0.410
10%TiO
2
0.66 10
3
0.608 0.390
Fig. 4. Impedance spectra of 10 wt% TiO
2
Composite polymer electrolyte at
different temperatures.
M. Ravi et al. / Polymer Testing 33 (2014) 152160 157
mobility. The rst effect which is evidenced fromthis gure
is that the Arrhenius plots of the composites do not break at
any higher temperature because the amorphous phase
extends down to ambient temperatures, exhibiting higher
conductivity values at these temperatures. There is also a
signicant conductivity enhancement, even in the high
temperature amorphous phase.
3.7. Cationic transference numbers
In order to substantiate the conductivity results further,
the cationic transference numbers of ceramic free polymer
electrolyte and nanocomposite electrolytes were
measured. The contribution of cations to the transference
number was measured using a combination of AC and DC
polarization techniques. Fig. 7 shows the typical impedance
plot of 10 wt% nano TiO
2
dispersed nano composite poly-
mer electrolyte lm at room temperature. Two semi cir-
cular arcs are observed in the impedance plots when
cation-reversible electrodes are employed. The second arc
is ascribed to a parallel total interfacial resistance (charge
transfer resistance R
ct
passive lm resistance R
p
) at the
reversible electrode- electrolyte interface. At room tem-
perature, the total interfacial resistance was found to be
fairly constant over a period of time, and hence the
contribution from R
p
has been neglected while evaluating
the transport number. The intercept of the high frequency
dispersion curve on the real axis gives the bulk resistance
R
b
of the material and second semicircle at the low fre-
quency region corresponds to the electrode electrolyte
charge transfer resistance R
ct.
Using the values of I
s
, R
b
and R
ct
cationic transport
number t
K
values were calculated with the formula:
t
K

R
b

V
Is

R
ct
where R
b
and R
ct
are the bulk and electrode-electrolyte
contact resistance determined from impedance spectra, I
s
the steady state current for a d.c bias 0.75 V volts. The
values of t
K

, t
IO

4
evaluated for the nano composite poly-
mer electrolytes are presented in Table 1. This suggests that
the interaction of inorganic llers and PVP chain with local
relaxation and segmental motion promotes a favorable
network for faster migration of the potassium ions. This in
turn causes enhancement of the mobility of the potassium
ions, resulting in increase of the potassium transference
number. This contributes to the improvement of ionic
conductivity of the PVP based nano composite polymer
electrolyte.
It has to be pointed out that the fraction of current
transported by the K

cations is lower than that of the IO

4

anions, and thus t

K

is usually of the order of 0.366 in

polymer electrolytes without nano ller. This is the
consequence of the structural position of the K

cations
which sit within a coiled PVP chain coordinating environ-
ment. In contrast to the relatively free movement of the
uncoordinated anions, the movement of these cations re-
quires relaxation and segmental motion of the chains, and
this explains their lower mobility.
The t
K

values obtained with this rened technique for

nano composite polymer electrolytes are reported in Table
1. The results are consistent in demonstrating a difference
in t
K

passing from the ller-free to the nanocomposite

polymer electrolyte. In addition, the t
K

values consistently
vary according to the Lewis acid character of the added
ller. For the most acidic type, i.e, the TiO
2
one, the trans-
ference numbers increase from 0.366 to 0.608 for ller free
(15 wt% KIO
4
complexed polymer electrolyte) to nano
composite polymer electrolyte at room temperature. These
values are consistent with action of the ceramic ller pro-
moting surface conducting pathways as a result of its Lewis
acid type interaction with the PVP chains. Potassium ions
are expected to move freely along these ceramic surface
pathways and thus, under these conditions, a consistent
enhancement of the cation transference number is logically
expected.
Hence, the role of the ller in the NCPEs is not limited to
the sole action of preventing crystallization of the polymer
chains but also, in particular, of promoting specic in-
teractions between the surface groups and both the PVP
segments and the electrolyte ionic species. These locally
induced structural modications result in the increase of
the fraction of free K

ions which can move rapidly

throughout the conducting pathways at the ceramic
extended surface. These modications result in enhance-
ment of the ionic conductivity over a wide temperature
range, as well as in the K

ion transference number. It

should be noted that these properties of NCPEs are partic-
ularly important in view of applications in practical batte-
ries. Similar behaviour was observed in a number of other
nano composite polymer electrolyte systems [8,2426].
3.8. Battery discharge characteristics
A polymer battery is a solid state battery in which the
electrolyte is salt complexed polymer lm and the negative
electrode is a metal foil. In the present investigation,
0 4000 8000 12000 16000
0
4000
8000
12000
16000
Z
"

O
h
m
s
Z' Ohms
R
b
4300
R
b
+R
e
16000
PVP:KIO
4
:TiO
2
(85:15:10)
Fig. 7. A.c. complex-impedance plot of K/NCPE/K cell.
M. Ravi et al. / Polymer Testing 33 (2014) 152160 158
cathode material contains three components: particles of
interaction material, normally called the active cathode;
particles of an electronic conductor such as carbon; and a
surrounding material consisting of polymer electrolyte,
which acts as an ionic conductor. These three components
together form the catholytic compartment. The choice of
anode in a solid state battery depends on the mobile spe-
cies in the electrolyte [27]. In the present case, potassium
metal was used as anode material.
Solid state electrochemical cells were fabricated in
the conguration K (anode)/(Polymer lm)/
(I
2
C electrolyte)(cathode) and their discharge char-
acteristics at ambient temperature for a constant load of
100 kU were shown in Fig. 8. The initial sharp decrease in
voltage may be due to the activationpolarization and/or the
formation of a thin layer of potassium at the electrode-
electrolyte interface [28]. The cell parameters such as
open- circuit voltage (OCV), short circuit current (SCC),
plateau region (the region in which cell voltage remains
constant), energy density etc. for all the cells are listed in
Table 2.
From the Table, it is clear the SCC and discharge times
for the plateau region were found to be greater in 10 wt%
TiO
2
nano composite cell compared to the other PVP:KIO
4
(85:15) complexed cells. This may be explained in terms of
high ionic conductivity and more amorphisity of 10 wt%
TiO
2
when compared to the other systems.
4. Conclusions
Nano composite polymer electrolyte lms were pre-
pared by a solution casting technique. The XRD data and
SEM shows the average particle size in the lm to be in the
nano region. The dispersed phase composite nature of the
polymer lms has been conrmed by FTIR and SEMstudies.
The dispersion of nano TiO
2
in the polymer host PVP:KIO
4
(85:15) resulted in ionic conductivity enhancement at
room temperature. The ionic conductivity increases with
increasing temperature as well as TiO
2
concentration. The
temperature dependance of ionic conductivity exhibited an
Arrhenius type process. The conducting species in this
polymer electrolyte systems were found to be predomi-
nantly ions, particularly cations. Using PVP:KIO
4
(85:15)
complexed and 10 wt% TiO
2
nano composite polymer elec-
trolyte systems, electrochemical cells were fabricated and
the discharge characteristics were studied. The 10 wt% TiO
2
nano composite cell showed better performance and sta-
bility in terms of the parameters OCV, SCC and discharge
time for the plateauregion. This is attributedtothe presence
of exible matrix and high ionic conductivity. These nano
composite polymer electrolyte systems are found to be po-
tential candidates for applications in solid state electro-
chemical cells.
Acknowledgement
One of the author Dr. M. Ravi is thankful to the Uni-
versity Grant commission for providing the nancial
assistance under the UGC-BSR Research fellowship for
Science meritorial students
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0 20 40 60 80 100 120 140 160 180
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