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Electrochimica Acta
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Effect of lithium salt concentrations on blended 49% poly(methyl methacrylate) grafted natural rubber and poly(methyl methacrylate) based solid polymer electrolyte
M.S. Suait a,b, , A. Ahmad a,b , H. Hamzah a,b , M.Y.A. Rahman c
a

Polymer Research Center, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia c College of Engineering, Universiti Tenaga Nasional, 43009 Kajang, Selangor, Malaysia
b

a r t i c l e

i n f o

a b s t r a c t
The effect of lithium salts (lithium tetrauoroborate, LiBF4 and lithium perchlorate, LiClO4 ) as doping salts in rubber-polymer blends, 49% poly(methyl methacrylate) grafted natural rubber (MG49) and poly(methyl methacrylate) (PMMA) in solid polymer electrolyte (SPE) lm for electrochemical devices application was investigated. The electrolyte lms were prepared via the solution casting technique using 025 wt.% lithium salt. The effect of the lithium salts on chemical interaction, ionic conductivity and structural and morphological studies of (70:30) MG49-PMMA lms was analyzed using Fourier Transform Infrared (FT-IR) Spectroscopy, Electrochemical Impedance Spectroscopy (EIS), X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Infrared analysis showed that the interactions between lithium ions and oxygen atoms occur at the ether group (COC) (15001100 cm1 ) on the MMA structure in both MG49 and PMMA. The oxygen atoms in the structure of the polymer host act as electron donor atoms and form a coordinate bond with the lithium ions from the doping salt to form polymersalt complexes. The ionic conductivity was investigated at room temperature as well as at a temperature range from 303 K to 373 K. The ionic conductivity without the addition of salt was 1.1 1012 S cm1 . The highest conductivity at room temperature for (70:30) MG49-PMMALiBF4 was 8.6 106 S cm1 at 25 wt.% of LiBF4 . The ionic conductivity of (70:30) MG49-PMMALiClO4 was 1.5 108 S cm1 at 25 wt.% of LiClO4 . However, both electrolyte systems do not exhibit Arrhenius-like behavior. Systems with LiBF4 salt have higher ionic conductivity than those with LiClO4 salt because of the differences in anionic size and lattice energy of the appropriate salt. The observations from structural and morphology studies showed that complexation and re-crystallization occur in the system. The XRD studies showed a reduction of the MMA peak intensity at 29.5 after the addition of 525 wt.% LiBF4 salt due to ion dissociation in the electrolyte system. Thus, this contributed to the increase of ionic conductivity in (70:30) MG49-PMMALiBF4 . Morphological studies showed that (70:30) MG49-PMMA is homogenously blended, and no phase separation occurred. The addition of lithium salts changed the topological texture from a smooth and dark surface to a rough and bright surface. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 30 November 2010 Received in revised form 5 June 2011 Accepted 6 June 2011 Available online xxx Keywords: 49% poly(methyl methacrylate)-grafted natural rubber (MG49) Ionic conductivity Lithium perchlorate (LiClO4 ) Lithium tetrauoroborate (LiBF4 ) Poly(methyl methacrylate) (PMMA) Solid polymer electrolyte

1. Introduction The observation of ionic conductivity in polymer materials complexed with salts by Fenton et al. [1] has led to the development of electrochemical device applications [2]. Thus far, research on poly(methyl methacrylate) (PMMA) based polymer electrolytes has only been conducted in 1985 by Iijima and co-workers [3]. PMMA

Corresponding author at: Polymer Research Center, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia. Tel.: +60 389215439; fax: +60 389215410. E-mail addresses: azizan@ukm.my, ady pfs@yahoo.co.uk (M.S. Suait). 0013-4686/$ see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2011.06.015

has been used as a polymer host due to its high stability at the lithium-electrolyte surface and because it is less reactive towards the lithium electrode [4]. It induces a more favorable passivation lm on the electrode surface. Therefore, a higher cyclability of lithium electrodes in PMMA-based electrolytes is expected. In addition, the MMA monomer in PMMA has a polar functional group in the main polymer chain that has a high afnity for lithium ions, which are transported. Oxygen atoms from the MMA structure will form a coordinate bond with the lithium ion from doping salts [5,6]. This polar group in the MMA acts as a stiffener that increases ion transport, which occurs through a continuous conduction path that does not affect the electrochemical stability of the electrolyte [7]. However, a plasticized gel-based PMMA electrolyte system

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Fig. 1. Structure of the MG monomer.

shows poor mechanical properties towards the electrode. This is because of the insufcient mechanical strength to hold the pressure between the anode and cathode. In this study, PMMA was blended with modied natural rubber to improve the mechanical properties and to overcome the brittle properties. Recently, modied natural rubber (NR), such as epoxidized NR (ENR) and PMMA-grafted NR (MG) based polymer electrolytes, has drawn the attention of many researchers [6,814]. Modied NR has attractive attributes, such as low glass transition temperature (Tg ); Tg ENR = 25 C, Tg MG49 = 60 C [8], soft elastomer characterization at room temperature and good elasticity. A suitable elasticity can result in at and exible lm. Therefore, an excellent contact is expected between an electrolytic layer and an electrode in a battery system. However, ENR has some drawbacks due to its mechanical properties, such as a slight stickiness and difculty peeling off of the substrate [9,12,15], compared to MG lm that is more free-standing, elastic and exible. However, modied NR, such as MG30 and MG49, has an oxygen atom in the MMA monomer, which can act as an electron donor atom in the structure of the polymer host. The oxygen atom with a lone pair of electrons forms a coordinate bond with the cation from metal salts, resulting in the formation of polymer-complexes [11,13]. MG49 was selected for this study because 49% is the highest percentage of PMMA that can be grafted on natural rubber, whereas that percentage is just 30% PMMA for MG30. Fig. 1 shows the structure of the MG monomer [14]. Furthermore, modied NR with a polar group can also act as a polymeric solvent, and the ionic conductivity is higher in comparison to the glassy or crystalline states of the polymer [2]. Previous studies on various MG rubbers have been conducted elsewhere [6,10,11,14]. Metal salts play an important role in ion-conducting electrolytes. Therefore, the selection of suitable metal salts, with regard to the cation and anion size, needs to be performed prior to the design of an electrolyte system. In this research, lithium salt was chosen because it contains the lightest properties of all metals, providing high gravimetric coulombic density despite having the low transition number of one electron per lithium atom [16]. The smaller cation size of the lithium ion could contribute to ion dissociation resulting from coulombic interaction forces between the two oppositely charged ions [17]. Other factors, such as cation polarity and a large anion size, are required for the delocalization of ionic charge, which could minimize the lattice energy [2]. Gray [2] and Shanshan Wang [18] explained that the anion size affects the solubility of the salts. High ionic conductivity can be achieved with the increase of anionic size, as shown below: Cl < I SCN < ClO4 CF3 SO3 < BF4 AsF6

Lithium salts, such as LiClO4 and LiBF4 , are used as dopants in polymer electrolyte systems because they can behave as a Lewis acid. Therefore, they can interact with electron donor centers. In addition, these types of salt have low lattice energy, which maximizes the ionic conductivity [19]. Other studies have reported that LiClO4 salt is very stable at ambient moisture and less hygroscopic in comparison to LiCF3 SO3 salt. LiClO4 salt gives a high solubility due to its low lattice energy value in plasticized solvent, with ionic conductivity around 104 to 103 S cm1 [20]. However, the high oxidation state of chlorine (VII) in perchlorate makes it a strong oxidant, which readily reacts with most organic species in violent ways under certain conditions, such as high temperature and high current charge [21]. LiBF4 is a salt based on an inorganic super-acid anion and has less toxicity in comparison to LiAsF6 and LiClO4 . In addition, BF4 anions possess high ionic mobility compared with other lithium salts, even though it has a lower dissociation constant than LiPF6 and LiAsF6 [22]. Takami et al. [23] found that thin lithium-ions batteries using LiBF4 salts give excellent performance and are very promising thin rechargeable batteries with high energy density, high discharge performance, very low swelling for high-temperature storage and excellent safety. In this work, MG49-PMMA polymer blends with a ratio of 70:30 were doped with lithium salts for the preparation of solid polymer electrolytes (SPE) by solution blending via the casting technique. All samples were characterized using Fourier Transform Infrared (FTIR) Spectroscopy, AC electrochemical impedances spectroscopy (EIS), X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). It was expected that the lithium salts would raise the conductivity in (70:30) MG49-PMMA polymer blends and the conductivity between LiBF4 and LiClO4 salts would be signicantly different. 2. Materials and methods 2.1. Materials MG49 was obtained under commercial name MEGAPOLY from Green HPSP (Malaysia) Sdn. Bhd., Petaling Jaya, Malaysia. PMMA with low molecular weight, as well as the LiClO4 and LiBF4 salts, were supplied by Fluka Chemicals, Germany. All the materials were used without further purication. 2.2. Sample preparation All samples were prepared by solution blending via the casting technique. MG49 was dissolved in stoppered asks containing toluene. After 24 h, the solution was stirred using efcient magnetic stirring for the following 24 h until complete dissolution of MG49 was achieved. PMMA solution was prepared in another stoppered ask containing toluene and stirred for 24 h. These two solutions were then mixed for 24 h to obtain a homogenous solution. LiClO4 salt was dissolved in THF solution for 12 h and added to the solution for the next 24 h with continuous stirring. The electrolyte solution was then cast onto a glass petri dish, and the solvent was allowed to slowly evaporate in a fume hood at room temperature. Residual solvent was then removed in a vacuum oven for 48 h at 50 C. The samples were then stored in a desiccator until further use. The same experimental procedure was repeated for different weight percents of LiClO4 and LiBF4 salt. 2.3. Characterization The FT-IR spectrum was recorded by a computer interfaced with a Perkin Elmer GX Spectrometer. The electrolyte was cast onto NaCl windows and analyzed in the frequency range of 4000 cm1 to

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400 cm1 , with a scanning resolution of 4 cm1 . The ionic conductivity measurements were carried out by EIS using a high frequency resonance analyzer (HFRA) model 1255 with applied frequency from 1 MHz to 0.1 Hz at 1000 mV amplitude. The conductivity measurements were conducted at room temperature at a temperature range of 303373 K. The 16 mm in diameter disc-shaped sample was sandwiched between two stainless steel block electrodes. The ionic conductivity ( ) was calculated from the bulk resistance (Rb ), which was obtained from the intercept on the real impedance axis (Z axis) and the lm thickness (l) and contact area of the thin lm (A = r2 = (1.60 cm/2)2 = 2.01 cm2 ), in accordance with the equation = [l/(ARb )]. The conductivity, dependence on temperature T, is given by the Arrhenius equation, = o e(Ea /kT) , where o , Ea and k represent the pre-exponential factor, activation energy and Boltzmann constant, respectively. The [O/Li+ ] ratio for the polymer blend was calculated by the following equation [24]: [O/Li+ ] = MT MW salt Msalt ((MW m /nm ) + (MW MG49 /nMG49 ) + (MW PMMA /nPMMA ))

3. Results and discussion 3.1. FT-IR analysis FTIR spectroscopy was used to observe the vibration energies of covalent bonds in the polymer host and the interactions that occur in the polymersalt complexes. Due to the fact that each type of bond has a different natural frequency of vibration, the identication of the absorption peak in the vibration portion of the infrared region gives a specic type of bonding [25,26]. The main regions of interest were the oxygen atoms of the carbonyl group (C O) (17501730 cm1 ) and the ether group (COC) (13001000 cm1 ) from the MMA structure in MG49 and PMMA [25]. According to the literature, the oxygen atoms in the structure of the polymer host act as electron donor atoms and form a coordinate/dative bond with the lithium ions from the doping salts to form a polymersalt [4,5,11,13,20,2731]. The vibration frequency of the polymersalt complexes is subsequently shifted to lower a wavenumber by about 1525 cm1 compared to the polymer hosts [25]. Fig. 2(a) and (b) shows the FT-IR spectrum of the symmetrical stretching of the carbonyl group, v(C O), from the MMA structure in the MG49-PMMA blend for LiClO4 and LiBF4 , respectively. The v(C O) frequency of MMA gave rise to an intense, very strong and sharp peak at 1733 cm1 . With the addition of 10 wt.% and 20 wt.% lithium salt in both systems, the intensity of the v(C O) of the MMA peak was reduced and shifted to 1735 cm1 . However, because the resolution was only within 4 cm1 , this result was not signicant enough to prove the interaction that occurs in the carbonyl group. The specic vibration mode of the ether group (COC) from the MMA structure in the MG49-PMMA blend for LiClO4 and LiBF4 could be observed at a stretching mode of COO and v(CO), a symmetrical stretching mode of vs (COC), an asymmetrical stretching mode of vas (COC) and an CH3 asymmetric deformation of MMA, (OCH3 ). However, the vibration at the stretching mode of COO and v(CO) at 1272 cm1 and at the symmetrical stretching mode of vs (COC) at 985 cm1 was not signicant enough to indicate the interaction that occurred. Fig. 3(a) and (b) shows the asymmetrical stretching mode of vas (COC) at 1150 cm1 for the MG49-PMMA blend. With the presence of 20 wt.% LiBF4 salts, the intensity of vas (COC) in MG49 systems reduced until it became lower than its neighboring peak at 1178 cm1 . The peak shifted approximately 28 cm1 from its original position. Furthermore, the peak shifts

where MT = total mass of the polymer (MG49 + PMMA) (g), Mw salt = the molecular weight of salt (g mol1 ), Msalt = the mass of salt (g), Mw m = the molecular weight of monomer (g mol1 ), Mw MG49 = the molecular weight of monomer MG49 (g mol1 ), Mw 1 PMMA = the molecular weight of monomer PMMA (g mol ), nm = the total number of oxygen atoms per repeated unit of monomer (MG49 + PMMA), nMG49 = the number of oxygen atoms per repeated unit of monomer MG49 and nPMMA = the number of oxygen atoms per repeated unit of monomer PMMA. XRD model D-5000 Siemen was used to observe the appearance and disappearance of the crystalline or amorphous phase with the presence of lithium salts. The data were collected in the range of diffraction angle 2 from 5 to 35 at a scanning rate 0.04 s1 . The surface morphology of the sample was observed by using the SEM model Philips XL30 with 1000 magnication at 20 kV electron beam. The sample was fractured in liquid nitrogen and coated with a gold sputtered-coated machine before the analysis. The analysis was carried out at room temperature.

100

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Wavenumber/cm

Fig. 2. FT-IR spectrum of the symmetrical stretching of the carbonyl group, v(C O) in (a) LiClO4 and (b) LiBF4 .

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80
LiClO4

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Fig. 3. FT-IR spectrum of the asymmetrical stretching of the ether group, vas (COC) in (a) LiClO4 and (b) LiBF4 .

observed in Fig. 4(a) and (b) suggests the asymmetric deformation of the MMA group, from (OCH3 ) of 1455 cm1 in the MG49PMMA blend to 1460 cm1 and 1461 cm1 for LiClO4 and LiBF4 , respectively. The interactions between the atoms were weaker due to the distraction that occurs on the molecule chain, indicated by the frequency of the infrared spectrum that was shifted to the left. The peak shift conrms the interaction between the lithium ions from the doping salt and the oxygen atoms in the structure of the polymer host. The reduction, with broadening of intensity and peak shift, indicates that the remaining vibration frequency between COCH3 bonding was disturbed by the interaction between the lithium ions and oxygen atoms. This is because a new bond was formed between the lithium ions from the doping salt and the oxygen atoms in the structure of the polymer host, also known as a

coordinate/dative bond, which led to the formation of polymersalt complexes [5,11]. The symmetric stretching of polyisoprene in the rubber chain of vs (C C) at 1604 cm1 showed no changes in terms of both the peak shift and intensity of the vibration for each sample [6]. This signies that there was no interaction with the non-polar group in the polymer chain. 3.2. Ionic conductivity The typical impedance spectra are shown in Fig. 5. The complex impedance spectra show two well-dened regions; a semicircle in the high frequency range that is related to the conduction process in the bulk of complex, and the linear region in the low frequency

80 LiClO4

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140 0

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Wavenumber/cm

Fig. 4. FT-IR spectrum of the asymmetric deformation of MMA at (OCH3 ) in (a) LiClO4 and (b) LiBF4 .

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Fig. 5. Impedance plot of SPE (70:30) MG49-PMMA with 0 wt.% to 25 wt.% (a) LiClO4 and (b) LiBF4 salt.

range that is attributed to the bulk effect of blocking electrodes. In an ideal case at low frequency, the complex impedance plot would show a straight line parallel to the imaginary axis; however, the curvature was caused by the double layer at the blocking electrodes [5,32]. No charge crossed the electrodes from the dielectric material to the metal electrode for the blocking contacts, and vice versa. The behavior of dielectrics under the application of steady voltage is mainly dependent on the type of contacts between the metal electrodes and the dielectric material. Therefore, the observed transient current was due to the polarization of the material, which may have been be caused by the hopping positive and/or negative charges in the polymer electrolytes system, as reported elsewhere [3335]. The impedance spectra for (70:30) MG49-PMMA with (a) 0 wt.% to 25 wt.% LiClO4 and (b) 0 wt.% to 25 wt.% LiBF4 are shown in Fig. 5. The impedance spectrum shows a semicircle in the high frequency range, which resulting a smaller value of bulk resistant with the addition of lithium salts. This indicates that the resistance within the material decreased with the increasing amount of charge carriers in the lithium salts. According to the equation = [l/(ARb )], the bulk resistance (Rb ) is the inverse of the ionic conductivity ( ). Therefore, the decrease of bulk resistance will increase the ionic conductivity of the polymer electrolytes. The ionic conductivity and [O/Li+ ] ratio of (70:30) MG49-PMMAlithium salts is shown in Table 1. The ionic conductivity without salt content was 1.1 1012 S cm1 . MG49-PMMALiClO4 salts gave rise to 1.5 108 S cm1 at 25 wt.% of LiClO4 . Meanwhile, the highest conductivity was observed at 8.6 106 S cm1 with LiBF4 salts at room temperature, with the same salt concentration and blend composition. The increase in ionic conductivity of LiBF4 was approximately 600 times higher than that of LiClO4 because of the difference in the anion size. The atomic radius (r) was calculated by Ue [22] using the van der Waals volume of each ion in the following equation: r = (3 V/4 )1/3 . In that study the atomic radius for BF4

was found to be 0.218 r/nm in comparison to ClO4 at 0.215 r/nm [22]. Gray [2] and Shanshan Wang [8] explained that the size of the anion affects the solubility of the salts. The large anion size is required for the delocalization of the ionic charge, which could minimize the lattice energy between the cation and anion. The smaller size of the lithium cation could contribute to the increase of ion dissociation resulting from coulombic interaction forces between the lithium cation and the large anion [17]. The ionic conductivity increased as the addition of salt increased to its maximum level in the polymer host. The conductivity was approximately 7.8 106 times higher after the addition of 25 wt.% LiBF4 salt to the polymer host. This was due to the increase of the number of conducting species in the electrolyte. The optimum value indicates the maximum and effective interactions between the oxygen atoms and Li+ ions in the electrolyte. This interaction was explained by FT-IR investigated by other researchers [5,6,1013,28]. It was discovered that a coordinate bond was formed in the complexes between the lithium ions and oxygen atoms from the polymer host. The maximum and effective interactions between oxygen atoms and lithium ions in the electrolyte system can be presented by the ratio of oxygen atoms to lithium ions and can be simply written as the [O/Li+ ] ratio. Different values of the [O/Li+ ] ratio could be due to the difference in molecular weight and weight percent of the lithium salt added. The ionic conductivity increased with increasing salt addition up to the maximum level in the polymer host due to the increasing LiBF4 salt content that contributed to the ion dissociation of LiBF4 salts into Li+ and BF4 species. The maximum and effective interaction for LiClO4 salt was [6/1]. Meanwhile, the maximum and effective interaction for LiBF4 salt was [5/1]. The increase of the conducting species in the electrolyte helped to increase the conductivity [27]. Moreover, the ionic conductivity only increased by about 1.3 104 after the addition of LiClO4 to the polymer host, which

Table 1 The ionic conductivity and [O/Li+ ] ratio (70:30) of MG49-PMMA-lithium salts at room temperature. Sample LiClO4 Ionic conductivity, 0 wt.% 5 wt.% 10 wt.% 15 wt.% 20 wt.% 25 wt.% 1.1 10 7.0 1011 1.2 1009 7.8 1009 1.4 1008 1.5 1008
12

LiBF4 (S cm
1

[O/Li ] ratio 30/1 15/1 10/1 8/1 6/1

Ionic conductivity, 1.1 10 4.0 1011 1.7 1008 5.2 1008 1.8 1006 8.6 1006
12

(S cm1 )

[O/Li+ ] ratio 29/1 14/1 10/1 7/1 5/1

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Fig. 7. XRD pattern of (70:30) MG49-PMMALiClO4 . Fig. 6. Arrhenius plot for the (70:30) MG49-PMMA electrolyte at 25 wt.% salt content.

is approximately 600 times lower than LiBF4 . As previously mentioned, LiBF4 (0.218 r/nm) has a larger anion size in comparison to LiClO4 (0.215 r/nm) [22]. The large anion size led to delocalization of the ionic charge that could have minimized the lattice energy between the Li+ and BF4 . Therefore, the ion dissociation of the smaller cation, Li+ could have increased, resulting from the weakening of coulombic interaction forces in the media. This weakening of coulombic interactions between opposite charges is described by the dielectric constant of the medium. The polarizability of a medium can arise from the polarizabilities of the atoms or molecules that it is composed of, even if they have no permanent dipole moment. Atoms or molecules that lack permanent dipoles have electronic polarizability, a tendency of electronic charge distributions to shift slightly within the atom, in response to an electric eld. The conductivity, dependence on temperature T, is given by Arrhenius equation: = o e(Ea /kT) , where o , Ea and k represent the pre-exponential factor, activation energy and Boltzmann constant, respectively. The value for o and Ea can be calculated from the y-axis and plot intercept between log and 1000/T [36]. Fig. 6 shows the dependence of conductivity on temperature by the Arrhenius plot for the MG49-PMMA blend at 25 wt.% LiClO4 and LiBF4 salts. It was observed that the conductivity increased with the increase of temperature from 303 K to 373 K. However, the relationship between conductivity and temperature was non-linear. This indicates that neither electrolyte system exhibited Arrhenius-like behavior. Therefore, the pre-exponential factor o and activation energy Ea of the electrolyte cannot be estimated from the plot. Non-Arrhenius-like behavior has been explained by Kincs and Martin [37], and the non-Arrhenius-like behavior was associated with dynamic temperature dependence restructuring of the anion sublattice. Meanwhile, Noor et al. [24] suggested that the value of Ea is due to the energy required to provide a conductive condition for the migration of ions. This is because the activation energy is a combination of the energy of the charge carrier creation (defect formation) and the energy of ion migration that can be evaluated by a linear t of the plot. However, Rajendran and Uma (2000) indicate that the non-Arrhenius-like behavior corresponding to ion transport in polymer electrolytes is dependent on the segmental motion of the polymer. Thus, the results may be effectively represented by the empirical VogelTammanFulcher (VTF) equation based on the free volume concept: = AT 1/2 exp B T To

where A and B are constants, T is the temperature in Kelvin (K) and To = (Tg 50), the temperature taken 50 K below the glass transition temperature (Tg ). Constant A in the VTF equation is related to the number of charge carriers in the electrolyte system, and constant B is related to the activation energy of ion transport associated with the congurational entropy of the polymer chains. The highest ionic conductivity for LiClO4 was 2.0 107 S cm1 at 373 K. However, the highest ionic conductivity for LiBF4 was 5.4 104 S cm1 , which is three magnitudes higher than that of LiClO4 at the same temperature. The bulk resistance of the electrolyte could not be observed above the impedance spectrum at this temperature because the sample was unstable in temperatures higher than 373 K. Rahman et al. [38] believed that the increased conductivity with temperature can be linked to the increasing chain exibility of the polymer chain in the electrolyte. Thus, increases the segmental motion of the polymer chain. This will lead to the increase in the dissociation rate of Li+ , thus improving the mobility of the charge carrier. Hence, the maximum conductivity of the electrolyte occurs at a temperature below the glass transition temperature (Tg ). However, the gap observed at temperatures above 343 K for LiBF4 and below 333 K for LiClO4 in Fig. 6 was due to the relaxation of the PMMA segment as reported by Othman et al. [36], after they plotted a loss tangent against temperature for the highest conductivity of PMMA-EC-LiBF4 samples. The -relaxation peak at 333 K was attributed to the main chain mobility below the glass transition temperature, Tg . This indicates that the increase in seg-

Fig. 8. XRD pattern of MG49-PMMALiBF4 .

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mental motion of the polymer chain will also enhance the transport of ions in the polymer blend, resulting in the conductivity enhancement for the LiBF4 system above the relaxation temperature, 333 K. However, the conductivity for LiClO4 was almost constant at 333 K, indicating that the segmental motion of the polymer chain does not affect the conductivity of LiClO4 salts. As can be observed by SEM micrograph in Fig. 9(c) and (e), the number of salt particles in the LiClO4 system was less than that observed in the LiBF4 system. If the remaining LiClO4 salt particles dissolve at high temperature,

it will lead to the complete dissociation of its ionic species. This signies that the number of conducting species has exceeded the maximum number of ionic species at this temperature. In addition, this observation may be due to the thermal decomposition of LiClO4 . Lu et al. [39] reported that the rst mass loss of LiClO4 salts was observed at 335 K, which is related to the removal of HCl and thermal decomposition reaction. The discharge of the oxygen element from LiClO4 during the decomposition process (oxygenation) could sometimes occur even under a nitrogen atmosphere, result-

Fig. 9. SEM micrograph of (70:30) MG49-PMMA at (a) 0 wt.%, (b) 15 wt.% and (c) 25 wt.% LiClO4 salt and (d) 15 wt.% and (e) 25 wt.% LiBF4 salt.

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ing in an overall exothermic effect. Meanwhile, the decomposition of LiBF4 requires energy to break some of its chemical bands. Therefore, the process showed endothermic behavior; in fact, LiBF4 salt is an ate-complex of LiF and BF3 . Consequently, they separate into their original composition at a high temperature, and the process is endothermic. From our preliminary studies on the MG49 solid polymer electrolyte [14], LiBF4 salt gives a higher ionic conductivity in comparison to LiClO4 salt due to the difference in anion size and lattice energy of the appropriate salt. LiBF4 salt has low lattice energy due to the delocalization of the charge of the large anion in comparison to that of the LiClO4 salt [2]. The size of the large anion as well as the low lattice energy of the lithium salt are generally expected to promote greater dissociation of the salts, and thus provides a higher concentration of ions to mobile [40]. In contrast, these ndings are slightly lower than the nding of Idris et al. [8] and Ali et al. [30] because in this work, no plasticizers such as polypropylene carbonate (PC) and ethylene carbonate (EC) were added into the electrolyte system, and a different type of lithium salt was used. The presence of PC and EC in polymer electrolyte can easily corrode the lithium metal electrode in the electrochemical cell [15]. 3.3. Structural studies The XRD analysis was used to determine the structure and crystallization of the polymersalt complexes by observing the appearance and disappearance of the crystalline or the amorphous region. The appearance of the amorphous region or the reduction of the crystalline region would give a high ionic conductivity in comparison to the crystalline or semi-crystalline region, as reported elsewhere [2,9,2831,40]. Fig. 7 shows the XRD pattern of (70:30) MG49-PMMALiClO4 . Meanwhile, Fig. 8 shows the XRD pattern of (70:30) MG49-PMMALiBF4 . From Fig. 7, pure LiClO4 salt gave highly intense peaks at 13.5 , 21.1 , 23.3 , 31.7 and 33.1 , and the presence of pure LiBF4 peaks can be observed at the angles of 13.5 , 18.8 , 21.5 , 23.6 , 26.8 , 28.2 , 32.0 and 32.8 . The introduction of lithium salts to the polymer host was found to decrease the semi-crystalline phase of MMA by reducing the MMA hump to a broad shape in the region between 10 and 20 . Meanwhile, an identical peak for MMA at the angle of 29.5 was found to decrease with the addition of LiBF4 salt. The presence of LiClO4 and LiBF4 peaks at a high salt concentration at the angles of 13.5 , 23.0 , 31.4 and 28.0 indicates that re-crystallization occurred in the polymer host. The re-crystallization of lithium salts occurred because of the ion association between the Li+ cation and the anion in the electrolyte at a high salt concentration [6]. Therefore, it provided low conductivity despite the addition of lithium salt to its maximum level [41]. Nevertheless, this nding is similar to those reported elsewhere, in which the ionic conductivity still occurred by either the reduction of the crystalline phase or the enhancement of the amorphous phase in the polymer host [2,6,2831,40]. The salt affects the overall ionic conductivity through the formation of crystalline complexes, the intramolecular cross-linking of the polymer chains and the degree of salt dissociation-number of charge carriers [2]. 3.4. Morphology studies Morphology studies were carried out by SEM to investigate the effect of lithium salt content on the fractured surface of the blended MG49-PMMA. Fig. 9 shows the SEM micrograph of MG49PMMA with (a) 0 wt.%, (b) 15 wt.% and (c) 25 wt.% LiClO4 salt and (d) 15 wt.% and (e) 25 wt.% LiBF4 salt. The SEM micrograph in Fig. 9(a) shows a homogenous surface of rubber-polymer blends using the solution blending technique. No phase separation could be observed by either physical observation or SEM in the blended

MG49-PMMA blank and blended MG49-PMMA with the addition of salt. This observation proves the existence of an intermolecular interaction between the oxygen atoms and the methylene group in the MMA structure [24]. The properties of exibility and elasticity of the blended lms were attributed to the polyisoprene segment in MG49, while the hard segment was contributed by the MMA monomer that has been grafted onto the rubber chain [27]. Monikowska et al. [42] suggested that the dark region in the SEM micrograph represents an amorphous phase. Meanwhile, the crystalline phase is contributed by the bright region in the polymer electrolyte system. In this study, the dark region was contributed by a rubber chain that has an amorphous characteristic. The bright region, which contributes to the crystalline phase, was given by the presence of PMMA and lithium salts. As can be observed in Fig. 9, the topological texture of blended MG49-PMMA changed from a smooth and dark fractured surface to a rough and brighter surface after the addition of lithium salt. The cross-sectional view of the sample in Fig. 9(c)(e) shows the formation of micro-pores due to the interaction between the solvent and the polymer host, as reported by Ahmad and co-workers [43]. The size of the micro-pores in Fig. 9(e) appears to be larger than the micro-pores in Fig. 9(d). According to [42], the presence of pores will give a compensating effect on the transporting properties of Li+ ions by increasing the surface area. Hence, it improves the conductivity of the electrolytes. The SEM micrograph in Fig. 9(e) also shows an increase of bright surface with the increase of pores size on the polymer host. The increment of the bright surface gives the crystalline properties in the polymer host. Further additions of lithium salt in this system will lead to the re-crystallization of lithium salt itself due to a high salt concentration in the electrolyte system. The high salt concentration gives a high tendency of the ionic species to associate or aggregate with each other [34,36,41,44]. This ionic tendency will decrease the number of the conducting species and the ionic mobility. Thus, it congests the ionic migration in the segmental polymer chain. This process will disturb the conducting process in the electrolyte systems and provide a low conductivity in the systems. 4. Conclusions The solid polymer electrolyte MG49-PMMA at the ratio (70:30) doped with two different lithium salts, LiClO4 and LiBF4 , was successfully prepared by a solution casting technique. The highest conductivity at room temperature was approximately 106 S cm1 at 25 wt.% of LiBF4 , which is two magnitudes higher than the ionic conductivity found in the LiClO4 system with the same concentration. This was due to the difference in the size of the anion and lattice energy of appropriate salt. Infrared analysis showed that the interaction between lithium ions and oxygen atoms occurred at the ether group (COC) (15001100 cm1 ) on the MMA structure in both MG49 and PMMA. The structural analysis recorded by XRD showed the reduction of the MMA crystallinity phase at the highest conductivity. The observations from the morphology studies by SEM showed that complexation and crystallization have occurred in the system. Acknowledgements The authors would like to extend their gratitude towards the Universiti Kebangsaan Malaysia for allowing this research to be carried out. This work is supported by the MOSTI grant 03-01-02SF0423. References
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Please cite this article in press as: M.S. Suait, et al., Effect of lithium salt concentrations on blended 49% poly(methyl methacrylate) grafted natural rubber and poly(methyl methacrylate) based solid polymer electrolyte. Electrochim. Acta (2011), doi:10.1016/j.electacta.2011.06.015