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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. Su’ait a,b,∗ , A. Ahmad a,b , H. Hamzah a,b , M.Y.A. Rahman c
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
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 tetraﬂuoroborate, 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) ﬁlm for electrochemical devices application was investigated. The electrolyte ﬁlms were prepared via the solution casting technique using 0–25 wt.% lithium salt. The effect of the lithium salts on chemical interaction, ionic conductivity and structural and morphological studies of (70:30) MG49-PMMA ﬁlms 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 (C–O–C) (1500–1100 cm−1 ) 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 polymer–salt 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 × 10−12 S cm−1 . The highest conductivity at room temperature for (70:30) MG49-PMMA–LiBF4 was 8.6 × 10−6 S cm−1 at 25 wt.% of LiBF4 . The ionic conductivity of (70:30) MG49-PMMA–LiClO4 was 1.5 × 10−8 S cm−1 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 5–25 wt.% LiBF4 salt due to ion dissociation in the electrolyte system. Thus, this contributed to the increase of ionic conductivity in (70:30) MG49-PMMA–LiBF4 . 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 12 June 2011 Keywords: 49% poly(methyl methacrylate)-grafted natural rubber (MG49) Ionic conductivity Lithium perchlorate (LiClO4 ) Lithium tetraﬂuoroborate (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.  has led to the development of electrochemical device applications . Thus far, research on poly(methyl methacrylate) (PMMA) based polymer electrolytes has only been conducted in 1985 by Iijima and co-workers . 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: email@example.com, ady firstname.lastname@example.org (M.S. Su’ait). 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 . It induces a more favorable passivation ﬁlm 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 afﬁnity 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 . However, a plasticized gel-based PMMA electrolyte system
High ionic conductivity can be achieved with the increase of anionic size. Recently. The same experimental procedure was repeated for different weight percents of LiClO4 and LiBF4 salt. LiBF4 is a salt based on an inorganic super-acid anion and has less toxicity in comparison to LiAsF6 and LiClO4 . the selection of suitable metal salts. However. Metal salts play an important role in ion-conducting electrolytes. the solution was stirred using efﬁcient magnetic stirring for the following 24 h until complete dissolution of MG49 was achieved. ENR has some drawbacks due to its mechanical properties. A suitable elasticity can result in ﬂat and ﬂexible ﬁlm. were supplied by Fluka Chemicals. such as LiClO4 and LiBF4 . such as a slight stickiness and difﬁculty peeling off of the substrate [9. such as high temperature and high current charge . PMMA was blended with modiﬁed natural rubber to improve the mechanical properties and to overcome the brittle properties. modiﬁed NR with a polar group can also act as a polymeric solvent.8–14]. The smaller cation size of the lithium ion could contribute to ion dissociation resulting from coulombic interaction forces between the two oppositely charged ions . providing high gravimetric coulombic density despite having the low transition number of one electron per lithium atom . Other studies have reported that LiClO4 salt is very stable at ambient moisture and less hygroscopic in comparison to LiCF3 SO3 salt. has drawn the attention of many researchers [6.10. such as MG30 and MG49. 2. Tg ENR = −25 ◦ C. very low swelling for high-temperature storage and excellent safety.14]. Other factors. with regard to the cation and anion size. Germany. Characterization The FT-IR spectrum was recorded by a computer interfaced with a Perkin Elmer GX Spectrometer. are required for the delocalization of ionic charge. The electrolyte solution was then cast onto a glass petri dish. high discharge performance. which readily reacts with most organic species in violent ways under certain conditions. This is because of the insufﬁcient mechanical strength to hold the pressure between the anode and cathode. an excellent contact is expected between an electrolytic layer and an electrode in a battery system. The samples were then stored in a desiccator until further use. shows poor mechanical properties towards the electrode. resulting in the formation of polymer-complexes [11. After 24 h. 1. LiClO4 salt gives a high solubility due to its low lattice energy value in plasticized solvent. Bhd. which can act as an electron donor atom in the structure of the polymer host. as well as the LiClO4 and LiBF4 salts. Structure of the MG monomer. Su’ait et al. soft elastomer characterization at room temperature and good elasticity. has an oxygen atom in the MMA monomer. Sample preparation All samples were prepared by solution blending via the casting technique. such as low glass transition temperature (Tg ). lithium salt was chosen because it contains the lightest properties of all metals. Petaling Jaya. modiﬁed natural rubber (NR). Fig. Residual solvent was then removed in a vacuum oven for 48 h at 50 ◦ C. which could minimize the lattice energy . The electrolyte was cast onto NaCl windows and analyzed in the frequency range of 4000 cm−1 to . AC electrochemical impedances spectroscopy (EIS). X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM).  found that thin lithium-ions batteries using LiBF4 salts give excellent performance and are very promising thin rechargeable batteries with high energy density. Therefore. These two solutions were then mixed for 24 h to obtain a homogenous solution. even though it has a lower dissociation constant than LiPF6 and LiAsF6 . Materials MG49 was obtained under commercial name “MEGAPOLY” from Green HPSP (Malaysia) Sdn.S. which maximizes the ionic conductivity . as shown below: Cl− < I− ∼ SCN− < ClO4 − ∼ CF3 SO3 − < BF4 − ∼ AsF6 − Lithium salts. PMMA with low molecular weight. In this research. In addition. Therefore. 1 shows the structure of the MG monomer . Materials and methods 2. MG49 was selected for this study because 49% is the highest percentage of PMMA that can be grafted on natural rubber. and the solvent was allowed to slowly evaporate in a fume hood at room temperature. are used as dopants in polymer electrolyte systems because they can behave as a Lewis acid. Tg MG49 = −60 ◦ C . Previous studies on various MG rubbers have been conducted elsewhere [6. these types of salt have low lattice energy. 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. Malaysia. LiClO4 salt was dissolved in THF solution for 12 h and added to the solution for the next 24 h with continuous stirring. Therefore.15]. PMMA solution was prepared in another stoppered ﬂask containing toluene and stirred for 24 h. Takami et al. MG49 was dissolved in stoppered ﬂasks containing toluene. In this work. 2.. In addition. elastic and ﬂexible. 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 signiﬁcantly different.124 M. The oxygen atom with a lone pair of electrons forms a coordinate bond with the cation from metal salts. However.11. 2. In this study. Modiﬁed NR has attractive attributes. / Electrochimica Acta 57 (2011) 123–131 Fig. whereas that percentage is just 30% PMMA for MG30. such as cation polarity and a large anion size.2. modiﬁed NR.13].1. such as epoxidized NR (ENR) and PMMA-grafted NR (MG) based polymer electrolytes. the high oxidation state of chlorine (VII) in perchlorate makes it a strong oxidant. BF4 − anions possess high ionic mobility compared with other lithium salts. with ionic conductivity around 10−4 to 10−3 S cm−1 . All samples were characterized using Fourier Transform Infrared (FTIR) Spectroscopy. Gray  and Shanshan Wang  explained that the anion size affects the solubility of the salts. However. Furthermore. needs to be performed prior to the design of an electrolyte system. and the ionic conductivity is higher in comparison to the glassy or crystalline states of the polymer . All the materials were used without further puriﬁcation. compared to MG ﬁlm that is more free-standing. they can interact with electron donor centers.12.3.
an asymmetrical stretching mode of vas (C–O–C) and an –CH3 asymmetric deformation of MMA. because the resolution was only within 4 cm−1 .M. Results and discussion 3. The [O/Li+ ] ratio for the polymer blend was calculated by the following equation : [O/Li+ ] = MT × MW salt Msalt × ((MW m /nm ) + (MW MG49 /nMG49 ) + (MW PMMA /nPMMA )) 3.13. The main regions of interest were the oxygen atoms of the carbonyl group (C O) (1750–1730 cm−1 ) and the ether group (C–O–C) (1300–1000 cm−1 ) from the MMA structure in MG49 and PMMA . is given by the Arrhenius equation.04◦ s−1 .1. With the addition of 10 wt. According to the literature.20. from the MMA structure in the MG49-PMMA blend for LiClO4 and LiBF4 . Mw −1 PMMA = the molecular weight of monomer PMMA (g mol ). The ionic conductivity ( ) was calculated from the bulk resistance (Rb ). Msalt = the mass of salt (g).27–31]. v(C O). Ea and k represent the pre-exponential factor.5. 2(a) and (b) shows the FT-IR spectrum of the symmetrical stretching of the carbonyl group. . 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 polymer–salt [4. 100 100 (a) 80 LiClO 4 80 LiBF 4 (b ) Transmittance (%) Transmittance (%) 60 60 10% 20% 0% 10% 40 0% 20% 40 20 20 1780 1760 1740 1720 -1 1700 1780 1760 1740 1720 -1 1700 Wavenumber/cm Wavenumber/cm Fig. The vibration frequency of the polymer–salt complexes is subsequently shifted to lower a wavenumber by about 15–25 cm−1 compared to the polymer hosts .S. ı(O–CH3 ). Mw salt = the molecular weight of salt (g mol−1 ). 3(a) and (b) shows the asymmetrical stretching mode of vas (C–O–C) at 1150 cm−1 for the MG49-PMMA blend. respectively. 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. Mw MG49 = the molecular weight of monomer MG49 (g mol−1 ). The peak shifted approximately 28 cm−1 from its original position. The conductivity measurements were conducted at room temperature at a temperature range of 303–373 K. The analysis was carried out at room temperature. The 16 mm in diameter disc-shaped sample was sandwiched between two stainless steel block electrodes.26]. Due to the fact that each type of bond has a different natural frequency of vibration.% and 20 wt. very strong and sharp peak at 1733 cm−1 . 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. in accordance with the equation = [l/(A·Rb )]. The conductivity.01 cm2 ). nm = the total number of oxygen atoms per repeated unit of monomer (MG49 + PMMA).1 Hz at 1000 mV amplitude. this result was not signiﬁcant enough to prove the interaction that occurs in the carbonyl group. The speciﬁc vibration mode of the ether group (C–O–C) from the MMA structure in the MG49-PMMA blend for LiClO4 and LiBF4 could be observed at a stretching mode of –COO– and v(C–O). The sample was fractured in liquid nitrogen and coated with a gold sputtered-coated machine before the analysis. activation energy and Boltzmann constant. Su’ait et al. Furthermore. the intensity of vas (C–O–C) in MG49 systems reduced until it became lower than its neighboring peak at 1178 cm−1 . Mw m = the molecular weight of monomer (g mol−1 ).% lithium salt in both systems. / Electrochimica Acta 57 (2011) 123–131 125 400 cm−1 . the identiﬁcation of the absorption peak in the vibration portion of the infrared region gives a speciﬁc type of bonding [25.% LiBF4 salts. which was obtained from the intercept on the real impedance axis (Z axis) and the ﬁlm thickness (l) and contact area of the thin ﬁlm (A = r2 = (1. The surface morphology of the sample was observed by using the SEM model Philips XL30 with 1000× magniﬁcation at 20 kV electron beam. However. FT-IR spectrum of the symmetrical stretching of the carbonyl group.60 cm/2)2 = 2. The v(C O) frequency of MMA gave rise to an intense. = o e(−Ea /kT) . the peak shifts where MT = total mass of the polymer (MG49 + PMMA) (g). The data were collected in the range of diffraction angle 2Â from 5◦ to 35◦ at a scanning rate 0. respectively. dependence on temperature T. a symmetrical stretching mode of vs (C–O–C). 2.11. v(C O) in (a) LiClO4 and (b) LiBF4 . With the presence of 20 wt. 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. with a scanning resolution of 4 cm−1 . Fig. However. where o . 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 polymer–salt complexes. the vibration at the stretching mode of –COO– and v(C–O) at 1272 cm−1 and at the symmetrical stretching mode of vs (C–O–C) at 985 cm−1 was not signiﬁcant enough to indicate the interaction that occurred. Fig. the intensity of the v(C O) of the MMA peak was reduced and shifted to 1735 cm−1 .
from ı(O–CH3 ) of 1455 cm−1 in the MG49PMMA blend to 1460 cm−1 and 1461 cm−1 for LiClO4 and LiBF4 . 4. The symmetric stretching of polyisoprene in the rubber chain of vs (C C) at 1604 cm−1 showed no changes in terms of both the peak shift and intensity of the vibration for each sample . 4(a) and (b) suggests the asymmetric deformation of the MMA group.126 M.11]. indicates that the remaining vibration frequency between C–O–CH3 bonding was disturbed by the interaction between the lithium ions and oxygen atoms. The peak shift conﬁrms the interaction between the lithium ions from the doping salt and the oxygen atoms in the structure of the polymer host. Ionic conductivity The typical impedance spectra are shown in Fig. Su’ait et al. The reduction. observed in Fig. with broadening of intensity and peak shift. which led to the formation of polymer–salt complexes [5.2. a semicircle in the high frequency range that is related to the conduction process in the bulk of complex. FT-IR spectrum of the asymmetrical stretching of the ether group. The complex impedance spectra show two well-deﬁned regions. respectively. This signiﬁes that there was no interaction with the non-polar group in the polymer chain. 3. vas (C–O–C) in (a) LiClO4 and (b) LiBF4 . / Electrochimica Acta 57 (2011) 123–131 80 LiClO4 (a) 80 LiBF4 (b) 20% 10% 70 70 Transmittance (%) 60 10% 20% Transmittance (%) 60 0% 50 0% 50 40 40 30 1200 1180 1160 1140 1120 1100 30 1200 1180 1160 1140 -1 1120 1100 Wavenumber/cm-1 Wavenumber/cm Fig. 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. The interactions between the atoms were weaker due to the distraction that occurs on the molecule chain. also known as a coordinate/dative bond. and the linear region in the low frequency 80 LiClO4 (a) Transmittance (%) LiBF 4 80 (b) 60 Transmittance (%) 60 20% 40 10% 0% 20 10% 20% 0% 40 20 0 1500 1480 1460 1440 1420 -1 1400 0 150 0 1480 1460 144 0 1420 -1 140 0 Wavenumber/cm Wavenumber/cm Fig. 3. FT-IR spectrum of the asymmetric deformation of MMA at ı(O–CH3 ) in (a) LiClO4 and (b) LiBF4 . . 5.S. indicated by the frequency of the infrared spectrum that was shifted to the left.
the complex impedance plot would show a straight line parallel to the imaginary axis. The maximum and effective interaction for LiClO4 salt was [6/1]. The conductivity was approximately 7.6.% 10 wt. Moreover. In that study the atomic radius for BF4 − was found to be 0. Sample LiClO4 Ionic conductivity.S.2 × 10−08 1.% LiClO4 and (b) 0 wt. The ionic conductivity and [O/Li+ ] ratio of (70:30) MG49-PMMAlithium salts is shown in Table 1. The optimum value indicates the maximum and effective interactions between the oxygen atoms and Li+ ions in the electrolyte. The increase of the conducting species in the electrolyte helped to increase the conductivity . No charge crossed the electrodes from the dielectric material to the metal electrode for the blocking contacts.5 × 10−8 S cm−1 at 25 wt. The impedance spectra for (70:30) MG49-PMMA with (a) 0 wt. This was due to the increase of the number of conducting species in the electrolyte. 5.8 × 10−09 1. as reported elsewhere [33–35].7 × 10−08 5. Therefore. Su’ait et al. range that is attributed to the bulk effect of blocking electrodes.% 15 wt.M. 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.8 × 106 times higher after the addition of 25 wt.% 25 wt. Impedance plot of SPE (70:30) MG49-PMMA with 0 wt.% 1.% (a) LiClO4 and (b) LiBF4 salt. the decrease of bulk resistance will increase the ionic conductivity of the polymer electrolytes. however.8 × 10−06 8. the observed transient current was due to the polarization of the material. The impedance spectrum shows a semicircle in the high frequency range. the curvature was caused by the double layer at the blocking electrodes [5.1 × 10 4. MG49-PMMA–LiClO4 salts gave rise to 1. Meanwhile.6 × 10−06 −12 (S cm−1 ) [O/Li+ ] ratio – 29/1 14/1 10/1 7/1 5/1 . In an ideal case at low frequency. Different values of the [O/Li+ ] ratio could be due to the difference in molecular weight and weight percent of the lithium salt added. According to the equation = [l/(A·Rb )].% 5 wt.4 × 10−08 1.6 × 10−6 S cm−1 with LiBF4 salts at room temperature. the highest conductivity was observed at 8.1 × 10−12 S cm−1 .% to 25 wt. Therefore.% LiBF4 are shown in Fig.10–13. with the same salt concentration and blend composition. 1. The atomic radius (r) was calculated by Ue  using the van der Waals volume of each ion in the following equation: r = (3 V/4 )1/3 .32].28].215 r/nm . The large anion size is required for the delocalization of the ionic charge. which Table 1 The ionic conductivity and [O/Li+ ] ratio (70:30) of MG49-PMMA-lithium salts at room temperature. which resulting a smaller value of bulk resistant with the addition of lithium salts. which could minimize the lattice energy between the cation and anion. 0 wt.% of LiClO4 .5 × 10−08 −12 LiBF4 (S cm −1 ) [O/Li ] ratio – 30/1 15/1 10/1 8/1 6/1 + Ionic conductivity. 5.2 × 10−09 7. 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. and vice versa. This indicates that the resistance within the material decreased with the increasing amount of charge carriers in the lithium salts.% to 25 wt. / Electrochimica Acta 57 (2011) 123–131 127 Fig. It was discovered that a coordinate bond was formed in the complexes between the lithium ions and oxygen atoms from the polymer host. the ionic conductivity only increased by about 1. which may have been be caused by the hopping positive and/or negative charges in the polymer electrolytes system. The ionic conductivity increased as the addition of salt increased to its maximum level in the polymer host.% LiBF4 salt to the polymer host.218 r/nm in comparison to ClO4 − at 0.% 20 wt. 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 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 . This interaction was explained by FT-IR investigated by other researchers [5.0 × 10−11 1. Meanwhile.1 × 10 7. The increase in ionic conductivity of LiBF4 was approximately 600 times higher than that of LiClO4 because of the difference in the anion size.3 × 104 after the addition of LiClO4 to the polymer host. the bulk resistance (Rb ) is the inverse of the ionic conductivity ( ). Gray  and Shanshan Wang  explained that the size of the anion affects the solubility of the salts. The ionic conductivity without salt content was 1.0 × 10−11 1. the maximum and effective interaction for LiBF4 salt was [5/1].% to 25 wt.
Noor et al. 6 was due to the ˇrelaxation of the PMMA segment as reported by Othman et al. and constant B is related to the activation energy of ion transport associated with the conﬁgurational entropy of the polymer chains. the relationship between conductivity and temperature was non-linear. in response to an electric ﬁeld. However. and the non-Arrhenius-like behavior was associated with dynamic temperature dependence restructuring of the anion “sublattice”. Meanwhile.  believed that the increased conductivity with temperature can be linked to the increasing chain ﬂexibility of the polymer chain in the electrolyte.  suggested that the value of Ea is due to the energy required to provide a conductive condition for the migration of ions. Fig.% salt content. XRD pattern of (70:30) MG49-PMMA–LiClO4 . 6. Ea and k represent the pre-exponential factor. Fig.218 r/nm) has a larger anion size in comparison to LiClO4 (0. The conductivity. is approximately 600 times lower than LiBF4 . the results may be effectively represented by the empirical Vogel–Tamman–Fulcher (VTF) equation based on the free volume concept: = AT − 1/2 exp −B T − To where A and B are constants. is given by Arrhenius equation: = o e(−Ea /kT) . XRD pattern of MG49-PMMA–LiBF4 . activation energy and Boltzmann constant. even if they have no permanent dipole moment.S. Tg . The large anion size led to delocalization of the ionic charge that could have minimized the lattice energy between the Li+ and BF4 − . where o . Thus. .128 M. 8. Non-Arrhenius-like behavior has been explained by Kincs and Martin . Atoms or molecules that lack permanent dipoles have electronic polarizability. 7. the temperature taken 50 K below the glass transition temperature (Tg ). As previously mentioned. the highest ionic conductivity for LiBF4 was 5.% LiClO4 and LiBF4 salts. LiBF4 (0.215 r/nm) . Thus. T is the temperature in Kelvin (K) and To = (Tg − 50). a tendency of electronic charge distributions to shift slightly within the atom. However. Therefore. Li+ could have increased. This indicates that neither electrolyte system exhibited Arrhenius-like behavior. Su’ait et al.0 × 10−7 S cm−1 at 373 K. However. Constant A in the VTF equation is related to the number of charge carriers in the electrolyte system. Rahman et al. thus improving the mobility of the charge carrier. dependence on temperature T. This indicates that the increase in seg- Fig. It was observed that the conductivity increased with the increase of temperature from 303 K to 373 K. This will lead to the increase in the dissociation rate of Li+ . . The value for o and Ea can be calculated from the y-axis and plot intercept between log and 1000/T . 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. The polarizability of a medium can arise from the polarizabilities of the atoms or molecules that it is composed of. Therefore. the gap observed at temperatures above 343 K for LiBF4 and below 333 K for LiClO4 in Fig. / Electrochimica Acta 57 (2011) 123–131 Fig. 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. after they plotted a loss tangent against temperature for the highest conductivity of PMMA-EC-LiBF4 samples.4 × 10−4 S cm−1 . The ˇ-relaxation peak at 333 K was attributed to the main chain mobility below the glass transition temperature. resulting from the weakening of coulombic interaction forces in the media. However. Hence. which is three magnitudes higher than that of LiClO4 at the same temperature. Arrhenius plot for the (70:30) MG49-PMMA electrolyte at 25 wt. respectively. 6 shows the dependence of conductivity on temperature by the Arrhenius plot for the MG49-PMMA blend at 25 wt. the pre-exponential factor o and activation energy Ea of the electrolyte cannot be estimated from the plot. This weakening of coulombic interactions between opposite charges is described by the dielectric constant of the medium. 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 ﬁt of the plot. the maximum conductivity of the electrolyte occurs at a temperature below the glass transition temperature (Tg ). The highest ionic conductivity for LiClO4 was 2. increases the segmental motion of the polymer chain. the ion dissociation of the smaller cation.
 reported that the ﬁrst mass loss of LiClO4 salts was observed at 335 K. Su’ait et al. As can be observed by SEM micrograph in Fig. this observation may be due to the thermal decomposition of LiClO4 .% and (c) 25 wt. 333 K. / Electrochimica Acta 57 (2011) 123–131 129 mental motion of the polymer chain will also enhance the transport of ions in the polymer blend. it will lead to the complete dissociation of its ionic species. 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. (b) 15 wt. However. indicating that the segmental motion of the polymer chain does not affect the conductivity of LiClO4 salts. SEM micrograph of (70:30) MG49-PMMA at (a) 0 wt. If the remaining LiClO4 salt particles dissolve at high temperature. Lu et al. the conductivity for LiClO4 was almost constant at 333 K.% LiClO4 salt and (d) 15 wt. result- Fig. the number of salt particles in the LiClO4 system was less than that observed in the LiBF4 system. This signiﬁes that the number of conducting species has exceeded the maximum number of ionic species at this temperature. . In addition. 9(c) and (e).% LiBF4 salt. resulting in the conductivity enhancement for the LiBF4 system above the relaxation temperature.% and (e) 25 wt.S.%.M. 9.
V.130 M. Meanwhile. 32.2◦ . as reported by Ahmad and co-workers . they separate into their original composition at a high temperature. This process will disturb the conducting process in the electrolyte systems and provide a low conductivity in the systems. no plasticizers such as polypropylene carbonate (PC) and ethylene carbonate (EC) were added into the electrolyte system. which contributes to the crystalline phase. 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◦ . was given by the presence of PMMA and lithium salts. the presence of pores will give a compensating effect on the transporting properties of Li+ ions by increasing the surface area. 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. 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 .5◦ . 3.% LiClO4 salt and (d) 15 wt. the process showed endothermic behavior. 7 shows the XRD pattern of (70:30) MG49-PMMA–LiClO4 . 23. 9(e) appears to be larger than the micro-pores in Fig. The observations from the morphology studies by SEM showed that complexation and crystallization have occurred in the system. The SEM micrograph in Fig. 26. According to .28–31. 28. As can be observed in Fig. LiClO4 and LiBF4 . while the hard segment was contributed by the MMA monomer that has been grafted onto the rubber chain . This ionic tendency will decrease the number of the conducting species and the ionic mobility. From Fig. the decomposition of LiBF4 requires energy to break some of its chemical bands. Therefore. From our preliminary studies on the MG49 solid polymer electrolyte .5◦ . Su’ait et al.5◦ was found to decrease with the addition of LiBF4 salt. The high salt concentration gives a high tendency of the ionic species to associate or aggregate with each other [34. 9. and thus provides a higher concentration of ions to mobile .0◦ .8◦ . / Electrochimica Acta 57 (2011) 123–131 ing in an overall exothermic effect.41. 9(a) shows a homogenous surface of rubber-polymer blends using the solution blending technique. This was due to the difference in the size of the anion and lattice energy of appropriate salt. which is two magnitudes higher than the ionic conductivity found in the LiClO4 system with the same concentration.8◦ . The bright region.S. The size of the micro-pores in Fig. LiBF4 salt is an ate-complex of LiF and BF3 . Consequently. Fig.% LiBF4 salt. .0◦ indicates that re-crystallization occurred in the polymer host. In contrast. Structural studies The XRD analysis was used to determine the structure and crystallization of the polymer–salt complexes by observing the appearance and disappearance of the crystalline or the amorphous region. The highest conductivity at room temperature was approximately ∼10−6 S cm−1 at 25 wt. as reported elsewhere [2. Meanwhile. 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. This work is supported by the MOSTI grant 03-01-02SF0423. 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.  suggested that the dark region in the SEM micrograph represents an amorphous phase. 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. Fig. 3. Fig. The increment of the bright surface gives the crystalline properties in the polymer host. The presence of LiClO4 and LiBF4 peaks at a high salt concentration at the angles of 13. J. Fenton.5◦ . 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 . 9(e) also shows an increase of bright surface with the increase of pores size on the polymer host.36. The cross-sectional view of the sample in Fig. 18. 7.6◦ . Infrared analysis showed that the interaction between lithium ions and oxygen atoms occurred at the ether group (C–O–C) (1500–1100 cm−1 ) on the MMA structure in both MG49 and PMMA. The salt affects the overall ionic conductivity through the formation of crystalline complexes. 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. 8 shows the XRD pattern of (70:30) MG49-PMMA–LiBF4 . and the presence of pure LiBF4 peaks can be observed at the angles of 13. and a different type of lithium salt was used.%.8◦ . 9(d). Monikowska et al. 23. and the process is endothermic. Conclusions The solid polymer electrolyte MG49-PMMA at the ratio (70:30) doped with two different lithium salts. 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. Wright. 9(c)–(e) shows the formation of micro-pores due to the interaction between the solvent and the polymer host. the dark region was contributed by a rubber chain that has an amorphous characteristic. these ﬁndings are slightly lower than the ﬁnding of Idris et al. 31. the intramolecular cross-linking of the polymer chains and the degree of salt dissociation-number of charge carriers . Meanwhile. this ﬁnding is similar to those reported elsewhere. the crystalline phase is contributed by the bright region in the polymer electrolyte system. 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 [2.1◦ . The SEM micrograph in Fig. 21. in fact.  and Ali et al. an identical peak for MMA at the angle of 29.1◦ . pure LiClO4 salt gave highly intense peaks at 13. 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. 23. In this study.M. was successfully prepared by a solution casting technique.9. Hence.5◦ .40]. Meanwhile. it provided low conductivity despite the addition of lithium salt to its maximum level . Parker. 31.4◦ and 28.7◦ and 33.0◦ and 32.3◦ . 9 shows the SEM micrograph of MG49PMMA with (a) 0 wt.% and (c) 25 wt. The presence of PC and EC in polymer electrolyte can easily corrode the lithium metal electrode in the electrochemical cell .% of LiBF4 . Polymer 14 (1973) 589. Acknowledgements The authors would like to extend their gratitude towards the Universiti Kebangsaan Malaysia for allowing this research to be carried out.40]. This observation proves the existence of an intermolecular interaction between the oxygen atoms and the methylene group in the MMA structure .  because in this work.4.% and (e) 25 wt. P. Thus. it improves the conductivity of the electrolytes. 21. (b) 15 wt. Therefore.E.3.6. References  D. 4.28–31. The structural analysis recorded by XRD showed the reduction of the MMA crystallinity phase at the highest conductivity. Nevertheless. The properties of ﬂexibility and elasticity of the blended ﬁlms were attributed to the polyisoprene segment in MG49. it congests the ionic migration in the segmental polymer chain.44].
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