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Advances in Polymer Science and Technology: An International Journal

Universal Research Publications. All rights reserved

Original Article
Ionic transport properties and characterization studies on Ag+ ion conducting polymeric nanocomposite electrolyte membrane (1-x) [70PEO:30AgCl]:xTiO2 prepared by hot press technique.
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Mohan L.Verma 1* & Arti Verma2

Condensed Matter Physics Research Laboratory, Department of Applied Physics Shri Shankaracharya College of Engineering and Technology Junwani, Bhilai (Chhattisgarh), INDIA, 490020, E-mail: cmprlssi@yahoo.com 2 Department of Applied Physics, Rungta College of Engineering & Technology Bhilai, Chhattisgarh, India Received 23 August 2011; accepted 13 September 2011

Abstract Study of ion transport property and characterization of nanocomposite polymeric membrane of composition (1-x) [PEO: AgCl]:xTiO2 where x = 3-10 (wt %). The maximum conduction is obtained for x=7 wt % of filler concentration. The nanocomposite polymer electrolyte (NCPE) membrane is casted by dispersing nanosize filler particles of TiO2 treated as 2nd phase in 1st phase solid polymer electrolyte (SPE) consists of polymer PEO & salt AgCl in appropriate weight % ratio. The maximum conduction of Ag+ ion in NCPE is obtained for x = 7 wt%. Activation energy Ea is calculated with the help of well known Arrhenius plot by least square fitting of the conductivity data. Characterization work is done with the help of XRD, DSC, and SEM study. 2011 Universal Research Publications. All rights reserved Key words: hot press technique, nanocomposite, polymeric membrane, activation energy. 1. Introduction: Present scenario in the field of battery is that most commercially available battery contains Li/Li + ions. Lithium has several operational limitations, viz difficult in handling in open ambient temperature due to high reactive material and they are very costly [1]. So the researchers are searching for new salt which may overcome these difficulties and can be used as the electrolytes for the battery. Solid materials which exhibit electric conduction through the migration of ions are called solid electrolytes these solids are also known as superionic solids which shows high ionic conductivity of the order of 10-2-10-6 S/cm and negligible electronic conductivity, low activation energy for ion migration at temperature much below their melting point. These materials include Ag+,Li+,Na+,o2-,Cu2+,H+,and F- ion conductors[2-3].Various attempts are made to frame high ionic conducting solid electrolytes. Now a days most of research work has been focused on development of polymeric and glassy electrolytes. But the glassy electrolyte have many disadvantages, they are brittle and have poor mechanical flexibility. Whereas polymer electrolytes have various advantages they are light weighted, they have good processibility, flexibility, elasticity, possibility of transparent thin film, relatively high ionic conductivity with low electronic conduction. A large number of polymer electrolytes with various ion conduction Ag+,Li+,Na+,o2-,Cu2+,H+,and F- etc have been reported since then[4]. These systems are based on polymer like polyethylene oxide (PEO), poly propylene oxide (PPO), poly vinyl alcohol (PVA), polyethylene succinate (PESc) etc. Polymer nanocomposite is the materials in which nanoscopic inorganic particles typically of size 10-100Ao are dispersed in organic polymer matrix in order to improve electrical performance of polymer. Polymer nanocomposite represent a new and better alternative to conventional polymer composite because of their nanosize, filler dispersed nanocomposite shows improved property as compare to pure polymer or traditional composites. Solid polymer electrolytes/nanocomposite electrolytes are prepared different methods one of them frequently used

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Advances in Polymer Science and Technology: An International Journal 2011; 1 (1): 10-13

method is solution cast method. This method has certain drawbacks, it require common solvent for dissolving complexing salt and polymeric host two solutions are mixed and poured into petridishes for drying by slow evaporation .this process is very lengthy process .recently developed new hot pressed technique for casting thin film for polymer based electrolytes to some extent is able to overcome drawbacks of solution cast method. This process is less expensive, comparatively takes less time, completely solvent free dry method for casting polymeric membrane [5, 6]. Present paper reports (i) casting of Ag+ ion conducting nanocomposite polymer electrolyte membrane of composition (1-x) [70PEO:30AgCl]:xTiO2 where x=3-10 (wt%) and to recognize a optimum conducting composition (OCC). For which the solid polymer electrolyte of composition [70PEO:30AgCl] is found as highest conducting film at room temperature has been identified as 1st phase polymer electrolyte host and nanosize TiO2 (particle size < 100 nm) filler particles as 2nd phase despersoid. (ii) The study of ion transport properties of nanocomposite polymeric electrolyte and to find activation energy values involved in ion transport by least square linear fitting of respectively log -1000/T Arrhenius plot. (iii) The material characterization studies. 2. Experimental techniques: 2.1 Material preparation: The casting of Ag+ ion conducting NCPE membrane (1-x) [70PEO:30AgCl]:xTiO2 where x=3-10 (wt %) was done using AR grade precursor chemicals: polyethylene oxide PEO (106 Mw, Aldrich, USA), Silver Chloride (AgCl) (purity>99%, Reidel lab reagent) and Titanium Oxide (TiO2) nanopowder (size< 100nm, Aldrich, USA). The powders of above mentioned chemicals in appropriate wt% ratio were homogeneously mixed for 30 min in an agate pestle mortar at room temperature then heated separately to temperature nearly 70C(close to melting point of PEO) for nearly 20 min by mixing continuously. The resulted slurry was then pressed (~1.25 tons/cm3) between two SS blocks giving rise to a film of uniform thickness 0.032cm. 2.2 conductivity () measurements: The conductivity () measurement was done with the help of (ESCORT ,ELC-131D,TAIWAN) by keeping different sample between two non blocking electrodes at fixed frequency (1kHz).The temperature dependent conductivity study of nanocomposite membrane is performed to calculate activation energy Ea. 2.3 phase/morphological characterization: For the structural and morphological characterization SEM is used. For the phase identification XRD study is done and for the thermal analysis DSC is performed. 3. Result and discussion: 3.1 Compositional variation of room temperature conductivity of NCPE membrane: Figure1 shows TiO2 (filler particle) concentration dependent conductivity of the nanocomposite polymer electrolyte

Figure 1: Room temperature conductivity log as a function of filler particle concentration (x) for NCPE membrane (1-x) [70PEO:30AgCl]:xTiO2

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membrane (1-x) [70PEO:30AgCl]:xTiO2 the conductivity measurement for the various composition x=3-10 (wt %) was done by dispersing nanosize filler particles of TiO2 (size < 100nm). The maximum conduction is obtained for x = 7% wt % (~1.610-7S/cm). It has been observed that by adding nanoscopic filler particles of TiO2 the conductivity of membrane enhances by two orders as compare to pure PEO. In some nanocomposite electrolytes Log - x variations contains two peaks which shows two types of conduction which can be explained on the basis of theories of nanocomposite electrolytes[8-9]. But in present work only single peak in Log - x curve is obtained. 3.2 Temperature variation of conductivity of NCPE membrane: Fig 2 shows the variation of conductivity as the function of inverse temperature for various composition of NCPE membrane (1-x) [70PEO:30AgCl]:xTiO2. It is found that from the graph (Log -1000/T) that the conductivity of SPE (for comparison) and NCPE membrane increases with the increase in temperature linearly. Conductivity () jump nearly at temperature 65-70C which shows the phase transition of PEO (polyethylene oxide) from semi crystalline to amorphous. The increase in conductivity with temperature can be interpreted as a hopping mechanism of coordinating sites, local structural relaxation and segmental motion of the polymer electrolytes complexes [10]. The straight line part of OCC of SPE and NCPE membrane can be expressed by Arrhenius equationNCPE OCC membrane: (T) = 0.46810-4 exp (-0.187/kT) Where activation energy Ea=0.187eV for NCPE (OCC). Figure 3 depicts the graph of activation energy (E a) and composition x (in wt %) of NCPE membrane of different composition. From the figure 3 it is clear that the activation energy Ea is minimum for the NCPE (OCC) composition. Advances in Polymer Science and Technology: An International Journal 2011; 1 (1): 10-13

Figure 2: Arrhenius plot for Log -1000/T plot for SPE [ 70PEO:30AgCl] and NCPE (1-x)[70PEO:30SgCl]:xTiO2 of different composition (x=3,5,7,9)

Figure 4: XRD pattern of (a) pure PEO, (b) SPE membrane [70PEO:30AgCl] and (c) NCPE membrane 93[70PEO:30AgCl]:7TiO2 observed from X-ray diffraction pattern that addition of TiO2 nanoscopic filler particles the some peaks of PEO becomes less prominent and their broadness increases which shows enhancement of plasticization of the electrolytes. 3.4 Thermal analysis: Fig 5 (a) & (b) shows DSC thermogram for SPE (OCC) membrane and NCPE (OCC) membrane respectively. The occurrence of an endothermic peak at 650C in SPE (OCC) is reduced in NCPE (OCC) slightly due to addition of nanoscopic filler. From the figure it can be observed that the crystallite melting temperature (Tm) for NCPE (OCC) membrane slightly decreases as compare to SPE (OCC) which may be possibly due to addition of nanoscopic fillers (TiO2). 3.4 Structural/morphological characterization: scanning electron microscopy (SEM) Figure 6(a) and (b) shows the SEM image of SPE (OCC) membrane [70PEO:30AgCl] and NCPE (OCC) membrane 93[70PEO:30AgCl]:7TiO2.The addition of TiO2 nano size filler has resulted in improved morphology of NCPE (OCC) membrane, since the filler particles occupied the pores and breaks the grain boundaries of (PEO-AgCl) complex and allows the transport of Ag+ ions in faster way. The two membranes are studied with the help of scanning electron micrograph. From the figure 6(a) & (b) it is clear that

Figure 3:activation energy (Ea) as a function of composition x (wt %) for NCPE membrane (1-x) [70PEO:30AgCl]:xTiO2 The increase in activation energy of NCPE (OCC) membrane indicates increase in mobility of the ions and it also indicates the increase in amorphousity of NCPE membrane by adding TiO2. 3.3 Phase identification of NCPE membrane: X-ray diffraction (XRD) Fig 4 shows X-ray diffraction pattern for polymeric host PEO, solid polymeric electrolyte (SPE) membrane and nanocomposite polymer electrolyte (NCPE) membrane. One can observe from XRD pattern that a prominent peak of PEO is shifted towards higher 2 values. Separate diffraction peaks of AgCl is not seen in diffraction pattern which indicates the complexation of AgCl with polymeric host PEO and does not remain as separate phase in electrolytes. It can also be

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Advances in Polymer Science and Technology: An International Journal 2011; 1 (1): 10-13

Figure 5: DSC thermograph of (a) SPE membrane [70PEO:30AgCl] and (b) NCPE membrane 93[70PEO:30AgCl]: 7TiO2. the surface of SPE membrane and NCPE membrane is smooth surface. 4. Conclusion: The membrane of solid polymer electrolyte of composition [70PEO:30AgCl] and nanocomposite membrane of composition 93[70PEO:30AgCl]:7TiO2 is casted by using hot press technique. For the transport property study conductivity () at room temperature and activation energy (Ea) calculated from temperature variation of conductivity for both the composition. For the phase identification XRD is done and for thermal analysis DSC studies are performed. For structural /morphological characterization SEM is done. From the Experiment it has been observe that the conductivity of NCPE (OCC) membrane enhances by one order as compare to SPE (OCC) and of two orders as compare to pure PEO. ACKNOWLEDGEMENTS The Authors are thankful to Chhattisgarh Council of Science and Technology, Raipur for providing financial assistance through the mini research project (Lett.N0.-356/CCOST/ MRP/09-04-08-09), to UGC-DAE consortium for scientific research Indore for providing lab facility and Dr. R.C. Agrawal, solid state Ionics lab, Raipur for providing valuable guidance. References: [1] Armond M.P.,Chabano JM and Duclot M P . Vashista et al (Amsterdom: North Holland) Fast Ion transport in Solids ed (1997)131 [2] F.Croce, G.B.Appetecchi L, Persi & B, Scrosate, nature, 394,456(1998) [3] Bruce, P.G., Solid State electrochemistry Cambridge University Press, Cambridge, 1995 [4] Nazri,G A and Pistoia Lithiumbatteries Science and Technology , Kluwer Academic publishers, New Yark,2004. [5] Appetecchi GB, Croce F, Persi L, Ronci F and Scrosati B Elevtrochim, Acta 45 (2000) 1481 [6] Appetecchi GB, Hassoum J, Scrosati B, Croce F, Cassel F and Solomon J. Power Sources 124 (2003) 246. [7] R.C.agrawal, Angesh Chandra, J Phy. Di Appl. Phys. 40, (2007) 7024 [8] J.Maier,Superionic Solids & Solid Electrolytes Recents Trends. [9] A.L. Lasker and S. Chandra (eds) (Acad, press ; New Yark) 137 (1989) [10] Jaipal reddy Ch V, Sharma A.K, Subba Rao U V, Solid State Ionics ,55,(1999) 126.

Source of support: Council of Science and Technology, Raipur, Mini Research Project (Letter. No: 356/CCOST/ MRP/09-04-08-09); Conflict of interest: None declared

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Advances in Polymer Science and Technology: An International Journal 2011; 1 (1): 10-13