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Physica B 403 (2008) 509516 www.elsevier.com/locate/physb

An investigation of PVdF/PVC-based blend electrolytes with EC/PC as plasticizers in lithium battery applications
S. Rajendrana, P. Sivakumarb,
b

Department of Physics, Alagappa University, Karaikudi 630 003, India Department of Physics, H.H. The Rajahs College, Pudukottai 622 001, India

Received 24 March 2007; received in revised form 12 June 2007; accepted 13 June 2007

Abstract Solid polymer electrolytes (SPEs) composed of poly(vinylidene uoride) (PVdF)poly(vinyl chloride) (PVC) complexed with lithium perchlorate (LiClO4) as salt and ethylene carbonate (EC)/propylene carbonate (PC) as plasticizers were prepared using solvent-casting technique, with different weight ratios of EC and PC. The amorphicity and complexation behavior of the polymer electrolytes were conrmed using X-ray diffraction (XRD) and FTIR studies. TG/DTA and scanning electron microscope (SEM) studies explained the thermal stability and surface morphology of electrolytes, respectively. The prepared thin lms were subjected to AC impedance measurements as a function of temperature ranging from 302 to 373 K. The temperature-dependence conductivity of polymer lms seems to obey VTF relation. r 2007 Elsevier B.V. All rights reserved.
Keywords: Polymer electrolytes; PVdF; PVC; Ionic conductivity; Lithium ion batteries

1. Introduction In recent years, solid polymer electrolyte (SPEs) have drawn keen interest due to their wide application in solidstate cells, sensors, electrochromic display devices, etc. Polymer electrolytes are mainly used as electrolytes in lithium batteries that exhibit a high level of energy storage. Such electrolytes were prepared using high molecular weight polymer with the addition of alkaline salt and organic solvents [1,2]. Generally, polymers are used as insulators; many polymers show low conductivity with 10121018 S/cm due to some contaminants such as solvents or ions. Moreover, these polymer electrolytes have exhibited ionic conductivities in the order of 104103 S/cm at room temperature [3,4] by the addition of plasticizers and salt. The ionic conduction in polymers is caused by the diffusion of the ion through their free volume. Therefore, ionic conductors should be obtained by dispersing several salts in polymers at molecular level [5]. It is quite obvious that the higher ionic conductivity about
Corresponding author. Tel.: +91 4565 225205; fax: +91 4565 225202.

E-mail address: p_psivakumar@yahoo.com (P. Sivakumar). 0921-4526/$ - see front matter r 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.physb.2007.06.012

103 S/cm could be obtained through a suitable composition of salt and plasticizers. The effect of plasticizers on the polymer electrolytes purely depends on the specic nature of the plasticizer, including viscosity, dielectric constant, polymerplasticizer interaction and ionplasticizers coordination. The choice of choosing ethylene carbonate (EC) and propylene carbonate (PC) as plasticizers is due to their higher dielectric constant as compared with other plasticizers. EC (dielectric constant e 89, boiling point 248 1C and viscosity Z 1.90 cp at 25 1C) and PC (dielectric constant e 64.4, boiling point 242 1C and viscosity Z 2.53 cp at 25 1C) are most promising and highly compatible with many polymers [69] and exhibit high conductivity of the order of X103 S/cm. To achieve higher conductivity at ambient temperature, many research works have been carried out with poly (acrylonitrile) (PAN) [10,11], poly(methyl methacrylate) (PMMA) [12,13], poly(vinylidene uoride) (PVdF) [14,15] and poly(vinyl chloride) (PVC) [16,17] as host polymer and incorporating inorganic lithium salt, EC and PC as plasticizers. Among these polymers, PVdF ([CH2CF2]n) is a technologically important semi-crystalline polymer and polymer electrolytes based on PVdF are expected to have

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high anodic stability due to strong electron withdrawing functional group [18]. PVdF has high permittivity, relatively low dissipation factor and high dielectric constant (e 8.4), which assist in greater ionization with lithium salt, providing a high concentration of charge carriers. PVC (dielectric constant e 3) is a commercially available polymer, which acts as good mechanical stiffener and is highly compatible with many polymers [19,20]. Periyasamy et al. [21] have made an electrochemical investigation on PVdF-based gel polymer electrolytes with the addition of EC and PC as plasticizers and reported the ionic conductivity to be in the order of 104103 S/cm and they also mentioned that certain lms were found to be fragile. In order to overcome this problem, Muniyandi et al. [22] optimized PVdF-based polymer electrolytes by blending PVC with 1:1 weight ratio of plasticizers (EC/PC) in different organic salts (LiAsF6, LiPF6 and LiBF4) and reported that PVdFPVC blend polymer electrolyte exhibits improved cyclic behavior. Vickraman and Ramamurthy [23] studied the blending effect of PVdF in the ionic transport mechanism of plasticized (EC/PC) PVCLiBF4based polymer electrolytes and reported that the blending leads to low conductivity. Further, they suggested that the PVdFPVC blend does not seem to be suitable as far as LiBF4 salt is concerned. In this aspect, the present investigation was carried out on PVdFPVC-based SPEs with different compositions of EC/PC as plasticizers and lithium perchlorate (LiClO4) as salt. The amount of polymers and salt were xed as followed in our earlier investigation [24]. It is well known that the lithium perchlorate has smaller ionic radius, smaller dissociation energy and is highly soluble in most of the organic solvents. Hence, LiClO4 was selected and used as a doping salt in this investigation. 2. Experimental 2.1. Materials PVdF and PVC with average molecular weights of 5.34 105 (Aldrich) and 1.5 105 (Aldrich), respectively, were used without further purication. LiClO4 anhydride was purchased from Aldrich, USA, and it was dried in vacuum at 100 1C for 24 h before use. PC and EC and tetrahydrofuran (THF) were purchased from Aldrich, USA and E-Merck, Germany, respectively, and used as received. The 4:1 weight ratio of PVdFPVC and 8 wt% of LiClO4 were dissolved in anhydrous tetrahydrofuran separately. These solutions were mixed together and the mixture was stirred continuously for 24 h with the addition of EC and PC for the ve different weight ratios (a) 80:20, (b) 60:40, (c) 50:50, (d) 40:60 and (e) 20:80 in total plasticizer weight (67 wt%). Then, this mixture was allowed to evaporate until a homogeneous gelly solution was obtained and it was cast on clean glass plates and Teoncoated bushes. PVdFPVCEC/PC blend-based polymer lm containing LiClO4 was obtained by heating at 50 1C

under reduced pressure for 46 h. Flexible thin lms with thickness of about 0.250.3 mm were obtained after casting. 2.2. FTIR and X-ray diffraction (XRD) studies FTIR spectra were recorded in the range 4000400 cm1 using Perkin-Elmer (Paragon 500 grating) IR spectrophotometer to identify the complexation behavior of the prepared polymer electrolytes. XRD spectra were recorded in Bruker-D8 advance diffractometer at a scan rate of 101/min to examine the crystallinity of the polymer electrolytes. 2.3. Scanning electron microscope (SEM) studies The SEM photographs of polymer electrolytes were recorded using JXA-840 SEM (JEOL, Japan) to study the surface morphology of the polymer lms. 2.4. TG/DTA analysis Thermal analysis of polymer lms was made using Perkin-Elmer (Pyres Diamond TG/DTA) at the heating rate of 101/min under nitrogen atmosphere from room temperature to 400 1C. 2.5. Conductivity measurements AC conductivity measurements were carried out on PVdF (20)PVC (5)EC/PC (67)LiClO4 (8) systems of about 50 mm thickness and 1 cm2 area. Polymer lms were sandwiched between two stainless steel (SS) electrodes under an oscillation potential of 10 mV from 40 Hz to 100 kHz using Keithley 3330 LCZ meter. The conductivity was calculated from complex impedance plots of measured impedance and phase angle. The temperature of the cell was controlled using a thermostat and the ionic conductivity was calculated by s t/(RbA), where Rb is the bulk resistance, t is the thickness of the lm and A is the area of the lm. 3. Results and discussion 3.1. Conductivity studies A typical complex impedance plot obtained in this study is shown in Fig. 1. The room temperature conductivities of these SPEs are mainly determined by the different weight ratio of EC/PC in PVdF (20)PVC (5)LiClO4 (8) complexes and are found to be $103 S/cm and these values increased up to 102 S/cm with increase in temperature (373 K) as is evident from Table 1. These values have increased two orders of magnitude as compared with PVdF (80)PVC (20)LiClO4 complex [24]. This complex impedance plot shows a slightly depressed slanted line. The bulk resistance Rb was obtained from the intercept of the

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(or position of the minimum value of Z00 ) the slanted line with the Z0 -axis. Conductivities of the polymer electrolytes were measured for the known values of bulk resistance (Rb), area (A) and thickness (t) of the electrolytes. In Fig. 1, the absence of the high-frequency semi-circular portion leads to the conclusion that the current carriers are ions and, therefore, the total conductivity is mainly the result of ion conduction. In other words, the ion diffusion inside the electrode results in a rapid decrease in resistance and it can provide a sufcient ion-conducting phase inside the electrodes to give a high capacitance and low ion-diffusion resistance, hence higher in conductivity [25]. From Table 1, it is concluded that room-temperature conductivities of all ve lms are nearly equal, which may be due to the migration of ions, which reached the equilibrium state. Fig. 2 illustrates the ionic conductivity of the polymer electrolytes as a function of temperature. Arrhenius plot suggested that there is no dynamic conformational change in the polymer matrix, and lithium ions might migrate through the conduction path, which was formed by the lattice structure of PVdF/PVC chain. The non-linear behavior of the polymer electrolyte is generally explained on the basis of VogelTammanFulcher (VTF) [2628] theory. Accordingly, the relationship between s and T is given by   E a s A0 T 1=2 exp , T T0
40 Z" imaginary (K. ohm) 35 30 25 20 15 10 5 0 0 5 10 15 Z'real (K. ohm)
Fig. 1. Impedance diagram of PVdF (20)PVC (5)LiClO4 (8) with different weight ratios: (a) 80:20 (b) 60:40 (c) 50:50 (d) 40:60 and (e) 20:80 of EC/PC in 67 wt%.

where the constant A0 is assumed to be independent of temperature, and T0 is the equilibrium glass transition temperature, which is close to the glass transition temperature (Tg) of the polymer electrolyte. It explains that the conductivity of the electrolytes at any particular concentration of EC/PC increases with increasing temperature. In fact, the ionic conductivity increases with decrease in activation energy. Fig. 3 shows the complex impedance plot of PVdF (20)PVC (5)LiClO4 (8) with the addition of 60:40 weight ratio of EC/PC in total plasticizer content (67 wt%) at different temperatures. It explains that the bulk resistance of the polymer electrolytes decreases with increasing temperature. Simply put, energy of ions transfer is reduced due to the plasticizer viscosity changes, which reects in ionic conductivity. In other words, the free volume approach for the ionic migration in the polymer chain leads to higher conductivity [8]. 3.2. XRD analysis XRD patterns of pure PVdF, PVC, LiClO4 and PVdF (20)PVC (5)LiClO4 (8) with the addition of EC and PC for ve different compositions ((a) 80:20, (b) 60:40, (c) 50:50, (d) 40:60 and (e) 20:80) are depicted in Fig. 4. X-ray diffraction peaks observed in Fig. 4ac indicate the semi-crystalline and crystalline phases of PVdF, PVC and
-1.6 Arrhenius plot

Impedance plot at room temperature

-1.8 Log () S/cm

(a) (b) (c) (d) (e)

-2 (a) -2.2 -2.4 -2.6 2.6 (b) (c) (d) (e)

20

25

30

2.8

3 1000/T (K-1)

3.2

3.4

Fig. 2. Arrhenius plot of log (s) against reciprocal temperature of PVdF (20)PVC (5)LiClO4 (8) with different EC/PC concentrations ((a) 80:20 (b) 60:40 (c) 50:50 (d) 40:60 and (e) 20:80).

Table 1 Conductivity values of PVdF (20)PVC (5)EC/PC (67)LiClO4 (8) polymer complexes Film Plasticizers content EC/ PC (67) 80:20 60:40 50:50 40:60 20:80 Conductivity values ( 103 S/cm) 303 K 3.873 4.683 4.352 3.353 3.401 313 K 4.052 5.012 5.142 3.821 4.506 323 K 4.873 6.479 7.915 5.525 4.921 333 K 5.891 9.476 9.124 7.784 6.872 343 K 7.305 11.79 12.23 11.17 8.373 353 K 8.694 13.10 15.06 11.78 10.56 363 K 10.56 14.21 17.57 13.41 13.33 373 K 13.21 14.58 18.02 13.76 15.62

a b c d e

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60 50 40 30 20 10 0 0 303 K 313 K 323 K 333 K 343 K 353 K 363 K 373 K

Impedance plot for various temperature

Z" imaginary (K.Ohm)

hence conductivity is higher. It reveals that the ionic conduction increases only in the amorphous phase. As reported by Ratner [29], it is found that the ionic conduction of SPE occurs primarily with the non-crystalline phase. Therefore, PVdFPVC-based electrolytes have achieved

10

20

30 Z' real (K. Ohm)

40

50

60

Fig. 3. Impedance plot of PVdF (20)PVC (5)LiClO4 (8) with 60:40 weight ratio of EC/PC in 67 wt% at different temperatures.

Fig. 4. XRD spectra of pure (a) PVC, (b) PVdF, (c) LiClO4 and PVdF (20)PVC (5)LiClO4 (8) with (d) 80:20 (e) 60:40 (f) 50:50 (g) 40:60 and (h) 20:80 EC/PC in 67 wt%.

LiClO4. But it seems that the intensity of peaks reduced in the polymer complexes, which are evident from Fig. 4dh. A higher degree of amorphous phase was observed in PVdF (20)PVC (5)LiClO4 (8) with 60:40 weight ratio of EC and PC in the total plasticizer content (Fig. 4f) system,

Fig. 5. SEM photographs of (a) PVC (25)(60:40) weight ratio of EC/PC (67)LiClO4 (8) (b) PVdF (80)PVC (20)LiClO4 (8) and (c) PVdF (20)PVC (5)(60:40) weight ratio of EC/PC (67)LiClO4 (8).

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good ionic conduction. It is observed that the relative sharp diffraction peaks at 2y 18.21, 19.71 and a broad peak centered at 2y 26.21 in pure PVdF are altered due to the incorporation of salt (LiClO4) and plasticizers (EC/PC). The rst two peaks are shifted as one broad peak at 2y 20.11 with less intensity and the broad peak at 2y 26.21 in pure PVdF completely minimized in all complexes. No peaks pertaining to lithium salt appeared in the complexes, which indicate the complete dissolution of lithium salt in the polymer matrices. These observations explain that the polymer undergoes signicant structural reorganization. 3.3. SEM studies The SEM images of (a) PVC (25)(60:40) weight ratio of EC/PC (67)LiClO4 (8) (b) PVdF (80)PVC (20)LiClO4

(8) and (c) PVdF (20)PVC (5)(60:40) weight ratio of EC/PC (67)LiClO4 (8) complexes are depicted in Fig. 5. The appearance of ne pores in Fig. 5a (i.e. the lm with PVC, salt and plasticizers alone) reveals the accumulation of plasticizers is very low in these regions, which is in accordance with the theory that PVC is immiscible with most of the plasticizers. In Fig. 5b, the effect of the addition of PVdF in the PVC matrix increases the pore size, and in Fig. 5c, the addition of plasticizers into the PVdFPVC blend shows a further increase in the pore size which could be due to the presence of the plasticizers in large amount with PVdF, as a result of the higher ionic conductivity. The pores in the micrographs indicate the occurrence of phase separation in the polymer electrolytes. The difference in the pore size is related to the difference in the driving for the phase separation [23,30]. It is concluded

Fig. 6. TG/DTA spectra of PVdF (20)PVC (5)LiClO4 (8) with (a) 80:20, (b) 60:40, (c) 50:50, (d) 40:60 and (e) 20:80 of EC/PC in 67 wt%.

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that the presence of plasticizer-rich phase shows a homogeneous pore structure, which leads to ion mobility, hence higher conductivity. 3.4. TG/DTA analysis In order to ascertain the thermal stability of the polymer electrolytes, the obtained lms were subjected to TG/DTA analysis. The study of PVdFPVCLiClO4 reported in our previous study [31] has been taken as the base for this investigation. The TG/DTA analyses of PVdF (20)PVC (5)LiClO4 (8) system containing ve different compositions of EC and PC are shown in Fig. 6. The lms appear to be quite dry since its weight is almost constant upto 98 1C. It is observed that the signicant weight loss of about 23%, which begins from the temperature of 98 to 102 1C, is attributed to the evaporation of foreign substance or moisture. After this loss, there is no decomposition upto162 1C. Then, there is a heavy weight loss of about 2025%, which may be due to the decomposition of PVdF in the electrolytes. No further weight loss is observed until the temperature reaches approximately 250 1C in TG curve. At 285 1C, 1012% of weight loss is observed, which is due to the rst decomposition of the electrolyte. From DTA curve, it is observed that the small endothermic peaks are observed below 98 1C and are attributed to the volatilization of monomers and oligomers adsorbed in the matrix can also be responsible for this initial weight loss [3234]. These polymer electrolytes suffered two stages of weight loss at about 156 and 286 1C and are due to the decomposition of PVdF and the evaporation of plasticizers, respectively. It is also identied that electrolytes have 50% of residual mass even after 300 1C, which are evident from Fig. 6. However, all electrolytes show similar behavior, Fig. 6d appears quite different. This thermogram shows a gradual weight loss of about 1012% upto 98 1C, which is due to the evaporation of moisture in the electrolyte. Above 100 1C, i.e. after complete dehydration, no further weight loss occurs till 156 1C. After this decomposition temperature, lm in Fig. 6d exhibits quite similar behavior like other electrolytes. The above analyses indicate that the PVdFPVC EC/PCLiClO4-based blend electrolytes are stable over 150 1C. Consistent with this thermal event, the weight has been constant upto 150 1C, thus the polymer electrolytes are stable upto 150 1C and are highly preferred in lithium polymer batteries as its operating temperature is normally in the range 4070 1C. 3.5. FTIR studies Molecular interactions between polymers, salt and plasticizers have been analyzed using FTIR spectra. The FTIR spectra of pure PVdF, PVC, LiClO4 and PVdF (20)PVC (5)LiClO4 (8) with the addition of EC and PC as plasticizers for ve different compositions are shown in

Fig. 7. The absorption peaks of CHQCH2 appearing at 1716 cm1, out of plane bending vibration and CH stretching frequency of vinyl group compound occurring at 961 and 2849 cm1, are found to be minimized to a maximum percentage and the absorption peaks of LiClO4 are minimized completely. The peaks appearing at 1224 and 840 cm1 are assigned to out-of-plane bending vibration of vinylidene group and wagging vibrations of PC molecules (QCH2) are shifted to 1219 and 836 cm1, respectively. Group frequencies at 1073 and 533 cm1 are ascribed to symmetric CC stretching and CF2 bending vibration of PVdF. It is observed that CCl stretching frequencies of PVC are found at 627 and 674 cm1 and it is attributed to a rotation in the helical structure of PVC, which is evident from Fig. 7dh. The rocking modes, which appeared at 840 and 879 cm1 are shifted to 836 and 879 cm1 in the polymer complexes (Fig. 8). The CF stretching of CF2 group is found at 1037 and 1183 cm1 and it disappears in the complexes, which may be due to the addition of plasticizers. This is in agreement with the nding of Watanabe et al. [35]. Peaks at 1482 and 720 cm1 are assigned to CH stretching and bending vibrations of

Fig. 7. FTIR spectra of pure PVdF, PVC, LiClO4 and PVdF (20)PVC (5)LiClO4 (8) with (a) 80:20, (b) 60:40, (c) 50:50, (d) 40:60 and (e) 20:80 of EC/PC in 67 wt% (range 4000450 cm1).

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Fig. 8. FTIR spectra of pure PVdF, PVC, LiClO4 and PVdF (20)PVC (5)LiClO4 (8) with (a) 80:20, (b) 60:40, (c) 50:50, (d) 40:60 and (e) 20:80 of EC/PC in 67 wt% (range 1000450 cm1).

Fig. 9. FTIR spectra of pure PVdF, PVC, LiClO4 and PVdF (20)PVC (5)LiClO4 (8) with (a) 80:20, (b) 60:40, (c) 50:50, (d) 40:60 and (e) 20:80 of EC/PC in 67 wt% (range 20001000 cm1).

CH2 groups. Peak found as a broad peak appearing at 840 cm1 is assigned to aliphatic group of CCl compound. Sharp vibrational peaks at 1774 and 1789 cm1 are assigned to CQO stretching vibrations of EC and PC, which have been shifted to 1765 and 1800 cm1 and they have been split into two small peaks (Fig. 9), which are attributed to the Fermi resonance of the CQO stretching mode with an overtone of the ring breathing mode and the existence of short-range ordering of the molecular orientation that originated from the dipoledipole coupling of two EC molecules [3638]. Fermi resonance occurred due to the coupling of two fundamental vibrational modes or the interaction between fundamental vibrations and overtones. CO stretching vibration of PC that occurred at about 13001100 cm1 completely disappeared. Broad peaks that occurred at 1645 and 879 cm1 are assigned to CQCF2 vibrations of vinylidene group. The absorption peaks at

2906 and 2978 cm1 are assigned to asymmetric stretching vibrations of methyl group in PC. These shifts in frequencies and modication of a singlet into a doublet and disappearance of some peaks on blending electrolyte lead to the occurrence of complex formation between polymers plasticizers. 4. Conclusion Blend-based PVdFPVC polymer electrolytes are prepared, and their physical and thermal properties are studied. The higher electrical conductivity was found to be 3.68 103 S/cm at room temperature in PVdF (20)PVC (5)(60:40) weight ratio of EC/PC (67)LiClO4 (8) complex and this is higher than the value reported by Vickraman and Ramamurthy [23]. We conclude that amount and nature of salt inuence the ionic conduction in the polymer electrolytes. The temperature dependence of ionic conductivity of these electrolytes exhibits VTF

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