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Journal of Molecular Liquids xxx (2011) xxx–xxx

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Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq

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Exerted influence of deep eutectic solvent concentration in the room temperature
ionic conductivity and thermal behavior of corn starch based polymer electrolytes
S. Ramesh a,⁎, R. Shanti a, Ezra Morris b
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Centre for Ionics University Malaya, Department of Physics, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, 53300 Kuala Lumpur, Malaysia

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a b s t r a c t

Article history:
Received 24 June 2011
Received in revised form 14 November 2011
Accepted 23 November 2011
Available online xxxx

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A series of biodegradable polymer electrolytes were fabricated by utilizing corn starch (CS), lithium bis(trifluoromethanesulfonyl)imide (LITFSI) and deep eutectic solvent (DES) (synthesized from the mixture of choline chloride and urea with 1:2 ratio) by solution casting technique. The incorporation of DES in plasticizing
the CS:LiTFSI matrix was valued primarily due to its capability in increasing the amorphous elastomeric phase
that is crucial in enhancing the ionic transport mechanism. The conductivity–temperature plot reveals the
nature of the cation transport which commensurates with Arrhenius rule. The highest conducting sample
was identified for the composition CS:LiTFSI:DES (14 wt.%:6 wt.%:80 wt.%) exhibiting the ionic conductivity
value of 4.56 × 10 − 3 S cm− 1 at 50 °C with activation energy of 8.22 kJ mol − 1. The relaxation frequency of
sample DES-80 is log ωm = 6.03 Hz, being the lowest relaxation time as revealed by the dielectric loss tangent
plot. The decreasing trends in the melting temperature of polymer electrolytes with increase in DES content
correlate to the occurrence of complexation that induces structural disorderliness. The heat-resistivity of
polymer electrolyte diminishes with the addition of DES and enhancement in the thermal stability was observed at the minimum DES content as revealed in TGA analysis.
© 2011 Published by Elsevier B.V.

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Keywords:
Deep eutectic solvent
Ionic conductivity
Melting temperature
Thermal decomposition

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1. Introduction

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The development of biodegradable polymer as host material has
attracted scientific and practical interest in recent years due to the environmental pollution attributed to the massive load of non-degradable
waste from synthetic polymer electrolytes. The only technique that
can be employed to dispose this type of polymer electrolytes is through
recycling which is neither practical nor economical. Thus, an effort was
evolved by substituting the synthetic polymer with the natural type, as
in this research corn starch (CS) is used as the replacement.
This effort could not be worked out by only utilizing the natural
polymer due to its highly crystalline nature that inhibits its employment in the development of high conducting polymer electrolytes.
Thus, CS based polymer electrolytes were developed with the combination of two different materials namely LiTFSI and DES in order to
obtain high conducting samples. This contraption was believed to
exert applicable electrical and other promising properties as desired.
The selected hydrophilic polymer gains its interest due to a number of
listed outstanding properties such as its water solubility, availability
of renewable resources, low cost, non-toxic and also biodegradable
nature [1–3].

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⁎ Corresponding author. Tel.: + 60 3 79674391.
E-mail addresses: rameshtsubra@gmail.com (S. Ramesh), shanthy87@yahoo.com
(R. Shanti), ezram@utar.edu.my (E. Morris).

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CS is a semi-crystalline polymer composed of both linear amylose
and branched amylopectin chain [4]. In order to enable the natural
polymer electrolytes to possess high ionic conductivity, the linear
monomer chain arrangement needs to be disrupted as an initial effort
allowing the matrix to be present in a highly amorphous state. The
initial step was accomplished upon the heating of CS in distilled
water. The heating procedure makes the starch granules to gradually
swell and undergo disruption into smaller aggregates or particles.
This results in the gelatinization of CS as the leaching of amylose
from the starch granules, evidence the diffusion in the amylose
chain [5,6].
The second monomer that needs to be disrupted in order to further enhance the ionic transport mechanism is the short-chain fraction of amylopectin. This monomer was arranged as double helices
in the form of highly crystalline order due to its branching nature
[4,7]. Thus, it is not easy to cause disorderliness in the arrangement
unless disrupted by negatively charged ions (anions). In order to
achieve this, two different types of additives were used to obtain
the anions for the disorderness purpose in this communication. The
first anion was TFSI − obtained from the complete dissolution of LiTFSI
in the polymer matrix. This type of anion is bigger in size thus it cannot contribute to greater structural disorderness which makes the CS:
LiTFSI polymer electrolytes to exhibit low ionic conductivity.
To further disrupt the branched monomer, another negative
charged ion which is smaller in size is needed to allow it to move in
between the condensed arrangement of atoms more freely and

0167-7322/$ – see front matter © 2011 Published by Elsevier B.V.
doi:10.1016/j.molliq.2011.11.010

Please cite this article as: S. Ramesh, et al., J. Mol. Liq. (2011), doi:10.1016/j.molliq.2011.11.010

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2 131 2. In this study. Experimental 146 103 2. the solid form chemicals will completely dissolve and appear as a colorless viscous solution. the mobile cations acquire high energy allowing frequent inter or intra-chain ion hopping and accordingly the ionic conductivity of the polymer electrolyte will be improved with rise in temperature from 50 °C to 100 °C.09 × 10− 4 4.3. The starting materials to synthesize DES are choline chloride and urea. The polymer electrolytes were then cast on a clean Teflon plate and dried in the oven at 55 °C for 8 h.22 70: 56: 49: 28: 14: 30:0 24:20 21:40 12:60 6:80 Fig.2. 60 and 80 wt. log [ωm (Hz)] Activation energy. electrochromic windows.1. et al.%) Ionic conductivity at 50 °C. 2. Materials 104 107 CS and LiTFSI were purchased from Aldrich and Fluka respectively. and solar-state batteries [12–16].3. dissipation factor and thermal properties. 3. DES-60 (■) and DES-80 (x). / Journal of Molecular Liquids xxx (2011) xxx–xxx Table 1 Composition ratio of CS:LiTFSI:DES system with the ionic conductivity. doi:10. The sample was heated sequentially from 25 °C to 500 °C at the heating rate of 10 °C min − 1 under an inert environment with the nitrogen flow rate of ca. and its non-toxic formulation and biodegradable nature [9–11]. Mol.98 × 10− 5 7. J. TGA analysis The thermal properties of polymer electrolytes were obtained by using the Mettler Toledo analyzer consisting of TGA/SDTA851 e main unit and STARe software.70 5. This type of ionic mixture gains its interest due to some of its unique properties including its unusual solvent property that further dissolves the highly crystalline CS.2. 50 ml min − 1.. relaxation frequency and activation energy (Ea) exhibited by polymer electrolytes with different DES content. its cheap cost compared to the ionic liquid due to the low cost of raw materials. The chosen anion is chloride (Cl −) which is more electronegative than TFSI −. The Cl − ions were obtained from the DES.55 8.1. After the heating process. an ionic mixture synthesized from choline chloride and urea in a specific ratio [8]. Instrumentation 100 101 enhance the amorphous nature in the polymer matrix.%. Arrhenius plots of log conductivity against reciprocal temperature for sample DES-20 (▲). Fig. σ ¼ σ o expð−Ea =KTÞ ð4:1Þ U 85 86 S. Upon synthesis. The nature of cation transport in the DES plasticized samples is quite similar to that in ionic crystals. solar cells. Please cite this article as: S.25 8. Distilled water is the solvent used to dissolve all the starting materials.010 134 135 136 137 140 141 142 143 144 145 147 148 149 150 151 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 . DES-40 (♦). Sample preparation The initial step in developing CS based polymer electrolytes is by dissolving an appropriate amount of CS powder as shown in Table 1 in 15 ml of distilled water and heat the milky solution till the temperature of 75 °C in order to gelatinize the CS.56 × 10− 3 – 4.2. mechanically free standing thin film for sample DES-0 and samples with lower DES content (DES-20 and DES-40) and consequently forms gel-like samples at higher plasticization (DES-60 and DES-80).03 – 13. (2011). E 96 97 R 94 95 R 92 93 O 91 C 89 90 N 87 88 F 2. The regression values (R2) that lie close to unity reveal the linear relationship that co-exists between these two parameters.00 6. Ramesh et al. The ion transport mechanism in polymer electrolytes can effectively be expressed as below: 154 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 t1:1 t1:2 t1:3 t1:4 t1:5 t1:6 t1:7 t1:8 O R O P D E 110 111 T 105 106 C 98 99 2. The analysis was carried out using an approximate of 5 mg of sample sealed in a 40 μl aluminium crucible. 138 139 102 2.1. 1. Synthesizing ionic mixture DES is synthesized by heating up the mixture of two individual solids which are choline chloride and urea in the ratio of 1:2 under manual stirring conditions using a hot plate.3.1016/j. Ea (kJ mol− 1) DES-0 DES-20 DES-40 DES-60 DES-80 2. σ (S cm− 1) Relaxation frequency.56 × 10− 5 9. Liq. Preparation of polymer electrolytes 3. Then an appropriate content of LiTFSI and the synthesized DES were added into the viscous solution and again the solution was allowed to stir for another hour to allow a good miscibility between the added chemical constituents. Impedance spectroscopy Impedance measurements were carried out at the temperature ranging from 50 °C to 100 °C using HIOKI Model 3532-50 Hi-Tester over the frequency range of 50 Hz to 5 MHz. 1 shows the variation of log ionic conductivity as a function of reciprocal temperature for plasticized polymer electrolytes with the DES content of 20. All the tested samples obey Arrhenius theory revealing that there is no phase transition in the plasticized polymer electrolyte matrix in the temperature range studied. 40.16 12.2. Temperature dependent conductivity studies 153 109 2.11.molliq. where mobile ions jump into neighbouring vacant sites [15]. This procedure yields sample in two different forms. the solution was cooled at ambient temperature under constant stirring for about 30 min. ease in the preparation method ignoring the purification process and no medium being required. Sample Polymer electrolyte (CS: LiTFSI:DES) (wt.3. This step yields a transparent viscous solution. Results and discussion 152 108 2. 132 133 2. This model explains that when the temperature of polymer electrolytes is increased. It can be verified that all the tested samples obey Arrhenius theory revealing that the conductivity mechanism is thermally assisted [14]. the suppression of the high crystallinity in CS matrix was scrutinized in terms of the temperature dependent ionic conductivity.10 6.2. purchased from Sigma.26 × 10− 5 4. DSC analysis The melting temperature of the prepared samples was visualized by using a METTLER TOLEDO Thermal Analyzer which comprised of DSC 823 e as the main unit and STARE software. The Cole–Cole impedance plot will be attained upon the completion of the analysis and this aid in plotting the ionic conductivity and tangent loss plots.1.3.2011. Ramesh. This analysis was carried out at the temperature ranging from 25 °C to 550 °C with the heating rate of 10 °C min− 1 under nitrogen atmosphere. This piece of effort enables the DES-plasticized sample to possess high ionic conductivity required for the application in electronic devices such as fuel cells.

Differential scanning calorimetry (DSC) E 201 202 increasing plasticization of DES. This was ascribed to the increase in the number of Li + ions that participates in the relaxation process to assist the ionic conductivity. a reduction in the melting temperature will be observed as more DES content is incorporated in the polymer electrolytes.45 86 82 80 88 t2:5 t2:6 t2:7 t2:8 .56 406. Ea is the activation energy and T is the absolute temperature in K. This was attributed to the increase in the amorphous elastomeric fraction in the CS:LiTFSI:DES matrix that facilitates fast Li + ion motion in polymer network upon increase in temperature [15. The outcome of this interaction persuades a disruption in the available crystalline fraction which increases the amorphocity of polymer electrolytes and allows the matrix to melt at lower temperature. The magnitude of tan δ also provides an informative insight on the number of Li + ions that participate in ion conduction [18].36 291.1016/j.11. Table 1 summarizes the activation energy (Ea) of polymer electrolytes with different DES content calculated from the slope of the Arrhenius plot. DES-0. enhancement in the ionic conductivity is observed. t2:2 Sample Temperature. From Fig.4. The increase in the magnitude of tan δ upon increase in DES content inferred to the increase in the area under the loss factor peak. 184 3. The reduction in the melting temperature of DES-0 compared to pure CS reveals the possible interaction between CS and LiTFSI [19]. Further decrease in melting temperature was observed upon incorporation of 20 wt. Mol.. Thus. more amorphous region will be available and facilitates the mobility of Li + ions in the matrix. The increase in DES content in polymer electrolyte increases the concentration of mobile Li + ions that participate in ion conduction while speeding up its mobility as it improves in the amorphous elastomeric phase. Liq. J.221 bile Li + ions coupled with greater mobility.69 Please cite this article as: S. DES-0. DES-20 and DES-80. Variation of tan δ with frequency for sample DES-80 at room temperature.12 257. Other plausible reasons for the displacement of loss tangent peaks to higher frequency may be correlated to the increase in the number of non-bridging ions in DES (Cl −) that act as a transit site for the mobility of Li + ions. Td loss. Frequency dependence of loss tangent studies 185 186 Figs. maximum decomposition temperature and total weight loss of pure CS. wt (%) Fig. frequent migrations of mobile ions are expected to occur which is crucial in enhancing the ionic conductivity. Ramesh et al. The observed decline in melting temperature was attributed to the enhancement in structural disorderness results of the complexation.010 317. Ramesh. DES-20 and DES-80 was summarized in Table 2 and the exhibited variation provides an insight on the constituent's miscibility which influences the structural properties. Sample DES-80 obtained the highest 220 ionic conductivity owing to the presence of high concentration of mo. Based on the tabulated results.2011. DES-20 and DES-80 as 253 Table 2 t2:1 The melting temperature. 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 Knowledge on the influence of both LiTFSI and DES content on the 251 CS matrix thermal properties was evaluated by the overlay thermo. Pure CS DES-0 DES-20 DES-80 313. 2. DES-0. The increase in the relaxation frequency (logmax ω) as a function of DES content is summarized in Table 1. 2 it can be observed that the loss tangent peaks were found to have shifted towards the higher frequency upon increase in DES content similar to sample DES-80 in Fig.3.252 gravimetric curves of pure CS. which increases the fraction of amorphous region. et al. Sample DES-80 exhibits the highest magnitude of tan δ compared to the rest of the tested samples attributed to the greater presence of Li + ions.S. it can be noted that the melting temperature of polymer electrolytes are reduced as more DES content is incorporated.molliq. Hence.16].57 236.67 382. thus a small amount of heat is sufficient to overcome the weak bonding in order to melt the amorphous natured polymer matrix. As more DES is incorporated into the CS:LiTFSI:DES matrix. 2 and 3 shed some light on the ionic transport mechanism in CS matrix when different concentration of DES is incorporated in CS: LiTFSI:DES system. T (°C) Total t2:3 weight Melting. It was observed that the melting temperature decreases with addition of LiTFSI and further declines with increase in DES content. DES-40 (◊) and DES60 (Δ) at room temperature. Thermogravimetric analysis 250 D P 3. it was found that Ea decreases with increase in DES content. Tm t2:4 Maximum decomposition. 224 225 3. The sample with lowest Ea value will exhibit the highest ionic conductivity due to greater migration of Li + ions. doi:10. This finding is evidence of the miscibility of DES in CS:LiTFSI matrix.2. (2011). / Journal of Molecular Liquids xxx (2011) xxx–xxx 182 183 where σo is a pre-exponential factor. 3. increase in ionic conductivity will be observed as 172 173 174 175 176 177 178 179 180 181 3 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 O R O 223 The melting temperature of pure CS. This verifies the complete miscibility of DES in CS:LiTFSI matrix which induces structural disorderliness.% DES in polymer electrolytes. The increase in Li + ion concentration evidences the efficiency of DES in overcoming the Coulombic force in LiTFSI. Variation of tan δ with frequency for samples DES-20 (□).50 261. 222 T 199 200 C 197 198 E 195 196 R 193 194 R 191 192 N C O 189 190 U 187 188 F Fig. 3. making more Li + ions to be available in enhancing the ionic conductivity. The atoms present in the amorphous region are weakly bonded. In view of the results. This transit site shortens the distance for Li + ions to hop from one oxygen atom to another in polymer chain acquiring less energy loss for the mobility of ion. Hence. The observation illustrates the reduction in the relaxation time of Li + ions due to greater acceleration on its mobility with increase in DES content [17]. Hence.

H. Chen. Electrochem. [5] Y. J. Angew.2011. Demiate. Miladinov. Capper. Norashikin. M. World Acad. Chem.Z. DES-20 (Δ) and DES-80 (x). Haihui. I. Hou. L. Alloin. the displacement of the maximum decomposition temperature to lower temperature reveals the decline in the samples heat-resistivity. [8] A.P. Subrahmanyam. It can be observed that the DES plasticized polymer electrolytes exhibited weight loss starting at temperature 100 °C.K. [7] W. an improvement in both the heat-resistivity and thermal stability of pure CS was observed upon incorporation of LiTFSI. Technol.% of DES in CS:LiTFSI matrix with the value 4. Jaipal Reddy. Mater.H. Further increase in DES content leads to the decline in both the heat-resistivity and thermal stability. V. having atoms that poorly coordinated. 88 (1988) 109–124. Y.K. Technol. which was almost 200 °C lower than those experienced by nonplasticized sample as in Fig. small amount of heat is sufficient to overcome the weak interactions between the connected atoms and hence decomposed at lower temperature. Electrochem. G. J. H. Choundhary. R.F. Takeda. Bu. 58 (2004) 641–649. Rajendran. T. B 108 (2004) 10845–10852. A. The melting temperature of polymer electrolytes decreases with the increase in DES content due to the occurrence of complexation that suppresses the crystalline phase. Ecletica Quim. X. 305 306 P R O O F 4. / Journal of Molecular Liquids xxx (2011) xxx–xxx 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 354 304 High conducting ‘green’ polymer electrolytes were synthesized by plasticizing the CS:LiTFSI matrix with DES. Based on the thermogravimetric curve of DES-0. Ramesh et al. Chem. Atwell. Ratner. Engl.S. Lacerda. The observed enhancement in heat-resistivity was correlated to the decomposition of the organic part in LiTFSI which induces the displacement of the maximum decomposition temperature to a higher level. Sci.molliq. [17] D. Cereal Chem. Li. Wan. 39 (2003) 70–71. 61 (2007) 3096–3099. [4] C. Conclusion References T 270 271 C 268 Q2 269 E 266 267 R 264 265 R 262 263 O 260 261 C 258 259 N 256 257 represented in Fig. M. Zhang. R.8. Y. Thermogravimetric curves for pure CS (◊). Feng. Pawlicka. Annu. E 4 [1] D. Chem. T. Hanna. C. C. Res. Schnitzler.P.C. Wu. J. Lett.O. D. H. et al. The displacement of the maximum decomposition temperature of sample DES-20 to lower temperature reveals the decline in the samples heat-resistivity. Cereal Food Worlds 33 (1988) 306–311.S. S.Y. Mol. 60 (2006) 3346–3349. Bioresour. A. Wong.A.L. Shriver. Gorecki.L. 246 (1993) 267–272. Z. Sanchez. M. [16] M. Conductivity–temperature plot reveals the cation transport mechanism that obeys Arrhenius rule.A. Brodwin. This incorporation improves the thermal stability of the polymer electrolytes which is evidenced by the reduction in total weight loss.M.C.R.F. 100 (2009) 2569–2574. Benqiao.010 296 297 298 299 300 301 302 303 307 308 309 310 311 312 313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328 329 330 331 332 333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351 352 353 . Papke. Dufresne. 4 have been recapitulated in Table 2. Davies.X. The continuous displacements of tan δ peak at higher frequency upon the increase in DES content suggest the increase in the ionic transport mechanism. Sivakumar. B. Further increase in DES content leads to the decline in both the heat-resistivity and thermal stability. Beninca. Varriano-Marston. Thermal properties are further altered upon addition of DES in polymer electrolytes. Lett. R. [6] W. M. Xingxiang. B.F. Abbott. Y. 48 (2009) 3486–3490. Ibrahim. 11 (2009) 209–211. This was associated to the presence of greater amorphous phase in the polymer electrolytes making it more heat sensitive. F. [19] M. [2] R. Paradhan. Int. Wang. Shriver.1016/j. Wu.Z. Since it is heat stable. Acta 53 (2007) 1404–1408. This was associated with the presence of greater amorphous phase in the polymer electrolytes making it more heat sensitive. reduction in heat-resistivity will be observed companied by the increment in total weight loss as more DES particles being eliminated out from the polymer electrolytes matrix upon the heating process [20]. D. Liq.K. Shan. 4.Y.R. M. Mater.F. Arof. Nevertheless this effort improves the thermal stability of the polymer electrolytes evident by the lesser total weight loss.B. [12] S.A.. L. Solid State Ionics 5 (1981) 83–88. Subba Rao.56 × 10 − 3 S cm − 1 at 50 °C and activation energy of 8. Rasheed.V. Siva Kumar. Y. Wong. [3] Y. 16 (1986) 245–261. Ed. less monomer will be detached from the complex structure. Xu. [9] Y. Li. reduction in heat-resistivity will be observed companied by an increase in total weight loss as more DES particles are decomposed from the polymer electrolyte matrix upon the heating process [20]. The diminishing in heatresistivity reasonably explains the possible structural disorderness in CS matrix that leads to the existence of high amorphous fraction U 254 255 294 295 D Fig. Thus. E.S.K. Commun. Wei.22 kJ mol − 1. 143 (2008) 154–159. Armand. D. 4.Z.A. W. Zobel. 4. [18] M. M. Wang.R. Ratner. M. [13] J. F. Lett. Azizi Samir. Sample DES-80 exhibits the highest relaxation frequency with the value of log ωm = 6. Rev. With reference to sample DES-20. 58 (2009) 176–180. D. U. S. H. S. The maximum enhancement in the ionic conductivity was achieved upon incorporating with 80 wt. [15] M. Mater. The maximum decomposition temperature and total weight loss being obtained from Fig.G. [20] A. J. Phys.L. Hizukuri. 81 (2004) 735–740. M. Jhong. J. [14] D. 33 (2008) 13–18. [11] J.S. S. X.11. Mol. Ionashiro. Lineback. A. Mater. DES-0 (□). T. Chem. Samantaray. doi:10. L. 76 (2009) 482–484. V. Yang. hence lowering the total weight loss. A.N.A. Carbohydr.L. 3 (2008) 597–608. F.Z. Please cite this article as: S. Hood.A. Subadevi. which easily decomposes at lower temperature.A. E. Wang. Sci. [10] H. Carbohydr. Eng. Hence. Polym. R. Commun. Electrochim. Apparently. Ning. P. Mohamad. Ding. Ramesh. TGA analysis reveals that the incorporation of DES in the polymer electrolytes significantly diminishes the heat-resistivity but an enhancement in the thermal stability occurs upon the minimum addition of DES. Rev. Carvalho Filho. Sci. The diminishing heat-resistivity explains the possible structural disorderness in CS matrix that leads to the existence of high amorphous fraction. Liq. Tambyrajah.F. Vieira.03 indicating its low relaxation time. Avellaneda. (2011). Int. Gu. Dupon. Tomooka. These reveal that the crystalline structures of the plasticized samples were not sustained due to the good miscibility of DES in CS:LiTFSI matrix. Zhang.