International Journal of Advances in Science and Technology, Vol. 3, No.

3, 2011

Studies on Magnesium Ion Conducting Polymer Electrolytes

J. Senthil1, O. Mahendran2, V. Meenakshisundaram3 and T. V. Krishnamoorthi4
1

Department of Physics, Tejaa Shakthi Institute of Technology for Women, Coimbatore, Tamil Nadu, India. senthilcsir@gmail.com
2

Department of Physics, Saraswathi Narayanan College, Madurai, Tamil Nadu, India.

3, 4

Department of Physics, Madura College, Madurai, Tamil Nadu, India.

Abstract
Preparation of magnesium polymer electrolytes has considerable attention in rechargeable batteries due to its abundance and inherent properties. Polymer electrolyte membranes comprising of poly (methyl methacrylate) (PMMA) and magnesium salts MgX (X = Cl2, F2 and Br2) were prepared by solvent casting technique. Fourier Transform Infra Red (FTIR) spectroscopic analysis reveals the ion interaction in the polymer matrix. The ionic conduction in the prepared polymer electrolytes was confirmed by impedance spectroscopic technique and it is found that ionic conductivity is of the order of 10-5 S cm-1 at ambient temperature. The surface morphology and homogeneity were investigated by scanning electron microscope (SEM). The thermal stability and glass transition temperature were investigated by differential scanning calorimety technique (DSC).

Keywords: Polymer electrolytes, Magnesium Salt, FTIR, SEM, Thermal and Conductivity Studies 1. Introduction
The most suitable battery type for consumers, battery that contains a large amount of energy in a small package, is light in weight and safe to use. In order to obtain superior secondary batteries with good cycle life performance, solid electrolytes are required for charge-discharge processes [1]. The characterization of ionic conducting polymers have been of considerable interest because of their commercial application in batteries, signal processing devices, semiconductors, fiber optics etc [2]. Many types of solid electrolytes based on organic polymer matrices which dissolve inorganic salts, especially alkalimetal salts have been investigated. However, little has been published for materials in which multivalent (di-, tri- and tetravalent) cations are the mobile species. Magnesium based higher energy devices have attracted attention due to the elements relative abundance, stability, low ionic radii compared to lithium, low equivalent weight, negative electrode potential, low toxicity, low price, ease of safe handling under ambient conditions etc. Thus, a solid state battery employing magnesium polymer electrolyte attracts considerable interest [3]. Several researchers have studied the gel polymer electrolytes (GPE) and reported as the most suitable electrolyte since their transport properties are quite exceptional. The reported gel polymer electrolytes are poly (acrylonitrile) (PAN), poly (methyl methacrylate) (PMMA), poly (vinylidene chloride) (PVC), poly (vinylidene fluoride) (PVdF), etc [1]. In practice, the choice of individual components in the electrolyte material is crucial, their chemistry and compatibility with each other and with the electrodes will affect both the mechanical and electrochemical properties of the material. A large number of studies have been carried out on polymer electrolyte based on PMMA containing the alkali metal salts for battery applications. Appetecchi [4] studied the kinetics and stability of the lithium electrode in PMMA based gel electrolytes. The physical properties of MgCl2 filled PMMA films for optical applications were reported by Abdelrazek [5]. Mitra et al [6] reported the composite ionic conductors based on magnesium salts and sol-gel derived silicate-tetraethylene glycol hybrids. Kushwaha et al [7] studied the preparation and characterization of magnesium ion conducting polymer composite films doped with Mg(ClO4)2. Pondey et al [8] investigated an ion-

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International Journal of Advances in Science and Technology, Vol. 3, No.3, 2011 conducting gel polymer electrolyte nanocomposites based on poly (vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) dispersed with nanosized magnesium oxide particles. Venkata Narayanan et al [3] studied the magnesium ion conducting molten electrolyte consisting of acetamide and magnesium perchlorate. In this work, PMMA-MgX (X = Cl2, F2 and Br2) polymer electrolytes were prepared by solvent casting technique. In order to characterize the prepared polymer electrolytes and to study the ion transport behavior in it, various physical experiments, namely, FTIR spectroscopy, impedance spectroscopy, scanning electron microscope and differential scanning calorimety have been carried out.

2. Experimental
PMMA with an average molecular weight of 1.7 x 105 (Aldrich) and Magnesium salts (MgCl2, MgF2 & MgBr2) (E-Merck) were dried by heating them under vacuum at 100C and 70C for 12h and 24h, respectively. Distilled Tetrahydrofuran (THF) (E-Merck) was used as the solvent for the polymer and salt. Slurries were prepared by prolonged mixing in a conical flask, using magnetic stirrer. The viscous solutions of the polymer and salt in THF were poured into a glass plate. The samples PMMA-MgX (X = Cl2, F2 & Br2) were dried by keeping in a vacuum oven at 40 C with a pressure of 10-1 torr for 48 hours. Then, the solvent free polymer electrolyte films were obtained. The FTIR (ABB BOMEN MB104) spectrometer measurements were made in the range 400 cm-1 to 4000 -1 cm . The ionic conductivity of polymeric membranes was measured from ac impedance (Keithley 3330 LCZ meter) studies at room temperature. Scanning Electron Microscope was used for micro structural studies and the glass transition temperature of PMMA-MgCl2 was found by DSC spectrum.

3. Results and discussion

3.1. FTIR spectroscopic studies
Infrared spectral analysis is a powerful tool to identify the nature of bonding and different functional groups present in a sample by monitoring the vibration energy levels of the molecules, which are essentially the fingerprint of different molecules. FTIR would be sensitive both in situations where complex formation has occurred in crystalline or amorphous phase. The FTIR spectrum of pure PMMA and polymer-salt complexes are shown figure 1. In pure PMMA FTIR spectrum (fig. 1), the weak absorption peaks appearing at (754, 843 and 987 cm-1; 1151, 1192 and 1244 cm-1; 1388 and 1444 cm-1; 2952 and 2997 cm-1) are assigned to C-H rocking, wagging, bending and stretching vibrations respectively. The strong absorption peak observed at 1732 cm-1 is assigned to C=O stretching vibrations of PMMA. The absorption peaks ranging from 3437 and 3616 cm-1, due to O-H stretching vibrations, are weak. The absorption peaks (754, 912, 966, 1064, 1147, 1190, 1238, 1275, 1436, 1734 and 2993 cm-1) observed in pure PMMA are shifted to (752, 1193, 1242, 1271, 1739 and 2995 cm-1) in PMMA-MgCl2 complex and (964, 1145, 1433 and 1743 cm-1) in PMMA-MgF2 complex and (910, 1066, 1141, 1272 and 1743 cm-1) in PMMA-MgBr2 complex spectrum. The absorption peaks at 1151, 1192 and 1244 cm-1 observed in pure PMMA are broadening in PMMA-MgX complexes. The sharp strong absorption peak, appearing at 1732 cm-1 in pure PMMA, is split into (1724 and 1739 cm-1) in PMMA-MgCl2 complex, (1716, 1728 and 1743 cm-1) in PMMA-MgF2 complex and (1716, 1728 and 1743 cm-1) in PMMA-MgBr2 complex spectrum. The peaks observed at 2952 cm-1 and 2997 cm-1 are broadening due to addition of magnesium salts in polymer complex. The peaks (1275 and 1365 cm-1) in pure PMMA are absent in PMMA-MgF2 and PMMA-MgBr2 complex spectrum respectively. And also several new peaks are found in polymer-salt complex spectrum The shifting of the intense peaks confirmed the interaction of salt in the structure of the polymer host to form a coordinate bond and subsequently forming polymersalt complexes. The intense, strong and sharp peak at 1732 cm-1 becomes split and broader with the addition of salt. This confirms the ion interaction in polymer matrix [9].

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3.2. Conductivity measurements

The complex impedance diagram of PMMA-MgF2 is shown in figure 2. The ionic conductivity of PMMA based polymer electrolytes calculated from { = d / (RA) } where d is thickness of the film, A is the surface area of the film and R is the bulk electrical resistance of the material which is obtained from the intercept on the real axis at the high frequency end of Nyquist plot of complex impedance. According to the theoretical analysis, two semicircles should appear in the impedance spectrum for a general symmetrical cell i.e. one at high frequency corresponding to the bulk electrolyte impedance and the other at lower frequencies related to the interfacial impedance. In the present work, the disappearance of the high frequency semicircular portion is the complex impedance plot let to a conclusion that the current carriers are ions and this leads one to further conclude that the total conductivity is mainly the result of ion conduction. The conductivity values of the prepared polymer electrolytes are shown in Table 1. It is observed that the ionic conductivity value of PMMAMgCl2 is high and it is found to be 1.95 x 10-5 S/cm. This reported value is in comparable with the values reported by Kushwaha et al [7] for composite polymeric films doped with Mg(ClO4)2 (1.2 x 10-3 S/cm) and Mitra et al [6] for PEG-MgCl2 (10-5 S/cm) complexes. This high value of conductivity for PMMA-MgCl2 complex, compared to other two complexes (table 3.1), may be due to its low molecular weight, high degree of dissociation, mobility of charge carriers and amorphosity of the system. In amorphous state the molecular packing is loose and weak. Thus, the polymer chain in this phase is more flexible and capable of orienting themselves relatively easily and rapidly. The increase in salt concentration may provide higher number of mobile charge carriers which is responsible for fast segmental motion. The fast segmental motion of polymeric chain reduces the relaxation time and increases ion transport properties. Hence it may be concluded that the major contribution mere to the ionic conductivity arises due to the incorporated magnesium salts in the polymer matrix. These results suggest that the ionic conductivity is affected by the diffusion rate of ion, which in turn depends on the size of each ion. The observed conductivity value of (10-5 S/cm) magnesium based solid polymer electrolytes are low by two orders of magnitude when compared to the lithium based solid electrolyteds (10-3 S/cm) [6, 7]. This decrease in conductivity may be due to the following reasons: 1) the high lattice energy (2326 kJ mol-1) of the salt which would result in the ionization being relatively lower 2) consumption of magnesium ions through the ion pair formation, which retards the mobility of charge carriers. The presence of the high molecular weight PMMA imparts a very high macroscopic viscosity to the system without significantly diminishing the conductivity. The addition of plasticizer or nano composites may increase the ionic conductivity of polymer electrolytes.

3.3. SEM analysis

The SEM micrographs of pure PMMA and PMMA-MgCl2 samples are as shown in figure 3 (a) and 3 (b) respectively. In the SEM image, the heterogeneous nature of the electrolyte appears. The addition of salt and filler in the PMMA polymer matrix disturbs the original structure of the polymer. The pores in the micrographs indicate the occurrence of phase-separation in the polymer electrolytes. The several pores or craters, which have formed on the surface, are due to the rapid evaporation of the solvent (THF). The difference in the pore size is related with the difference in the driving force for phase separation. It can be observed that the size of pores is decreased when the PMMA content increased [9]. The surface of PMMA-MgCl2 sample is slightly smooth and homogenous and is expected to continue in the bulk. Hence, magnesium ions can traverse through the sample easier compared to other sample resulting in our sample being more conductive.

3.4. DSC analysis

The DSC curve for PMMA-MgCl2 sample is shown figure 4. A special case in which the temperature of a phase transformation is of great importance in polymers is the glass transition temperature, Tg. This is the temperature at which amorphous (noncrystalline) polymers are converted from a brittle, glasslike form to a rubbery, flexible form. Since the mechanical behavior of polymers changes markedly at the glass transition temperature, it is an important characteristic of every polymer. In the DSC experiment, Tg is manifested by a drastic change in the base line, indicating a change in the heat capacity of the polymer (Fig. 4). From DSC curve of PMMA-MgCl2, the

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International Journal of Advances in Science and Technology, Vol. 3, No.3, 2011 glass transition temperature (Tg) is found to be 23 C. The cation-chlorine binding energy, which is the driving force for salt dissolution, contributes to the increase in the barrier to the rotation of polymer segments. This is evidenced by marked decrease in glass transition temperature for polymer-salt complexes.

4. Conclusion
Magnesium based PMMA-MgX (Cl2, F2 and Br2) polymer electrolyte systems have been prepared by solvent casting technique. FTIR studies indicate the co-ordination of salts with polymer. The conductivity of the solid electrolytes is of the order of 10-5 at room temperature. SEM analysis has been made in PMMA-MgCl2 polymer electrolyte. The glass transition temperature is found by DSC technique. The magnesium ion conducting polymer electrolytes are promising solid electrolytes for solid state magnesium secondary batteries.

5. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] Song J Y, Wang Y Y, Wan C C, Review of gel-type polymer electrolytes for lithium-ion batteries, J Power Sources, vol. 77, pp. 183-197, 1999. Deepak Kumar and Hashmi S A, Ionic liquid based sodium ion conducting gel polymer electrolytes, Solid State Ionics, vol. 181, pp. 416-423, 2010. Venkata Narayanan N S, Ashok Raj B V, Sampath S, Magnesium ion conducting, room temperature molten electrolytes, Electrochemistry Communications, vol. 11, pp. 2027-2031, 2009. Appetecchi G B, Croce F, Scrosati B, kinetics and stability of the lithium electrode in PMMA based gel electrolytes, J Electrochimica Acta, vol. 8, pp. 991-997, 1995. Abdelrazek E M, Physical properties of MgCl2-filled PMMA films for optical applications, Physica B vol. 351, pp. 8389, 2004. Sagar Mitra and Srinivasan Sampath, Solgel derived, magnesium based ionically conducting composites, J Materials Chemistry, vol. 12, pp. 2531-2537, 2002. Kushwaha S S S Mishra J, Preparation and characterization of magnesium ion conducting glasspolymer composite films, Research Communications, Current Science vol. 88, pp. 1159-1162, 2005. Pandey G P, Agrawal R C and Hashmi S A, Magnesium ion-conducting gel polymer electrolytes dispersed with nanosized magnesium oxide, Journal of Power Sources, vol. 190, pp. 563-572, 2009. Rajendran S, Ramesh Prabhu M and Usha Rani M, Characterization of PVC/PEMA Based Polymer Blend Electrolytes, J Electrochem Sci., vol. 3, pp. 282 290, 2008. Rajendran S, Mahendran O, Krishnaveni K, Effect of CeO2 on Conductivity of PMMA/PEO Polymer Blend Electrolytes, J New Mat Electrochem Systems, vol. 6, pp. 25-28, 2003. Rajendran S, Mahendran O and Kannan R, Ionic conductivity studies in composite solid polymer electrolytes based on PMMA, Material Chem and Phys, vol. 74, pp. 52-57, 2002. Pandey GP, Agrawal RC, Hashmi SA, Electrical and electrochemical properties of magnesium ion conducting composite gel polymer electrolytes, J Physica D, vol. 43, pp. 255501, 2010. Peter P. Chu and Jaipal Reddy M, Ion pair formation and its effect in PEO:Mg solid polymer electrolyte system, Journal of Power Sources, vol. 109, pp. 340346, 2002. Masayuki Morita et al., Ionic conductance behavior of polymeric electrolytes containing magnesium salts and their application to rechargeable batteries, Solid State Ionics, vol. 152 153, pp. 259 266, 2002. Levi M.D. et al., Microelectrode studies of reversible Mg deposition in THF solutions containing complexes of alkyl aluminum chlorides and dialkyl magnesium, Journal of Electroanalytical Chemistry, vol. 576, pp. 183195, 2005.

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Figure 1. FTIR spectra of polymer electrolytes

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Figure 2. Complex Impedance diagram of PMMA-MgF2

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Table 1. Conductivity values of polymer complexes

Polymer Complexe PMMA-MgX

Ionic Conductivity ( S/cm)

X = Cl2

1.95 x 10-5

X = F2

0.31 x 10-5

X = Br2

0.16 x 10-5

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Figure 3. SEM Photograph of (a) pure PMMA (b) PMMA-MgCl2 film

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Figure 4. DSC curve for PMMA-MgCl2 polymer complex

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