MOLLIQ-03396; No of Pages 4

Journal of Molecular Liquids xxx (2011) xxxxxx

Contents lists available at SciVerse ScienceDirect

Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Q1 3
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Exerted inuence 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
a
b

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

a r t i c l e

i n f o

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

A series of biodegradable polymer electrolytes were fabricated by utilizing corn starch (CS), lithium bis(triuoromethanesulfonyl)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 conductivitytemperature plot reveals the
nature of the cation transport which commensurates with Arrhenius rule. The highest conducting sample
was identied 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 m = 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.

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 scientic 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 [13].

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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
rst 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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2.3.1. 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. The ColeCole impedance plot will be attained upon the completion of the analysis and
this aid in plotting the ionic conductivity and tangent loss plots.

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2.3.2. 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 analysis was carried out using an approximate of 5 mg of sample sealed in a 40 l aluminium crucible. 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 ow rate of ca. 50 ml min 1.

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2. Experimental

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2.1. Materials

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CS and LiTFSI were purchased from Aldrich and Fluka respectively.

The starting materials to synthesize DES are choline chloride and
urea, purchased from Sigma. Distilled water is the solvent used to dissolve all the starting materials.

2.3.3. 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. 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.
3. Results and discussion

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2.2. Preparation of polymer electrolytes

3.1. Temperature dependent conductivity studies

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2.2.1. 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. Upon synthesis, the
solid form chemicals will completely dissolve and appear as a colorless viscous solution.

Fig. 1 shows the variation of log ionic conductivity as a function of

reciprocal temperature for plasticized polymer electrolytes with the
DES content of 20, 40, 60 and 80 wt.%. The regression values (R2) that
lie close to unity reveal the linear relationship that co-exists between
these two parameters. It can be veried that all the tested samples
obey Arrhenius theory revealing that the conductivity mechanism is
thermally assisted [14]. The nature of cation transport in the DES plasticized samples is quite similar to that in ionic crystals, where mobile ions
jump into neighbouring vacant sites [15].
This model explains that when the temperature of polymer electrolytes is increased, 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.
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. The ion transport mechanism in polymer electrolytes can effectively be expressed as below:

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t1:1

t1:2
t1:3

t1:4
t1:5
t1:6
t1:7
t1:8

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2.2.2. 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. This step yields a transparent viscous solution. After the heating process, the solution was
cooled at ambient temperature under constant stirring for about
30 min. 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. The polymer electrolytes
were then cast on a clean Teon plate and dried in the oven at 55 C
for 8 h. This procedure yields sample in two different forms, mechanically free standing thin lm 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).

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2.3. Instrumentation

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enhance the amorphous nature in the polymer matrix. The chosen

anion is chloride (Cl ) which is more electronegative than TFSI .
The Cl ions were obtained from the DES, an ionic mixture synthesized from choline chloride and urea in a specic ratio [8]. 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, its cheap cost compared to the ionic liquid due to the
low cost of raw materials, ease in the preparation method ignoring
the purication process and no medium being required, and its
non-toxic formulation and biodegradable nature [911]. 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, solar cells, electrochromic windows, and solar-state batteries [1216].
In this study, the suppression of the high crystallinity in CS matrix
was scrutinized in terms of the temperature dependent ionic conductivity, dissipation factor and thermal properties.

o expEa =KT

4:1

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S. Ramesh et al. / Journal of Molecular Liquids xxx (2011) xxxxxx

Table 1
Composition ratio of CS:LiTFSI:DES system with the ionic conductivity, relaxation frequency and activation energy (Ea) exhibited by polymer electrolytes with different
DES content.
Sample Polymer
electrolyte (CS:
LiTFSI:DES) (wt.%)

Ionic
conductivity at
50 C,
(S cm 1)

Relaxation
frequency, log
[m (Hz)]

Activation
energy, Ea
(kJ mol 1)

DES-0
DES-20
DES-40
DES-60
DES-80

2.26 10 5
4.98 10 5
7.56 10 5
9.09 10 4
4.56 10 3

4.70
5.10
6.00
6.03

13.16
12.55
8.25
8.22

70:
56:
49:
28:
14:

30:0
24:20
21:40
12:60
6:80

Fig. 1. Arrhenius plots of log conductivity against reciprocal temperature for sample
DES-20 (), DES-40 (), DES-60 () and DES-80 (x).

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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where o is a pre-exponential factor, Ea is the activation energy and T

is the absolute temperature in K.
Table 1 summarizes the activation energy (Ea) of polymer electrolytes with different DES content calculated from the slope of the Arrhenius plot. Based on the tabulated results, it was found that Ea
decreases with increase in DES content. 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 [15,16]. The sample with lowest Ea value
will exhibit the highest ionic conductivity due to greater migration
of Li + ions.

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3.2. Frequency dependence of loss tangent studies

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Figs. 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. From Fig. 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. The increase in the relaxation frequency (logmax ) as a function of DES
content is summarized in Table 1. 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]. As more DES is incorporated into the CS:LiTFSI:DES matrix, more amorphous region
will be available and facilitates the mobility of Li + ions in the matrix.
Hence, enhancement in the ionic conductivity is observed.
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. 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, frequent migrations of mobile ions are expected to occur which is crucial in enhancing the ionic
conductivity.
The magnitude of tan also provides an informative insight on the
number of Li + ions that participate in ion conduction [18]. The increase in the magnitude of tan upon increase in DES content inferred to the increase in the area under the loss factor peak. This
was ascribed to the increase in the number of Li + ions that participates in the relaxation process to assist the ionic conductivity. The increase in Li + ion concentration evidences the efciency of DES in
overcoming the Coulombic force in LiTFSI, making more Li + ions to
be available in enhancing the ionic conductivity. Sample DES-80 exhibits the highest magnitude of tan compared to the rest of the tested samples attributed to the greater presence of Li + ions.
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. Thus, increase in ionic conductivity will be observed as

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The melting temperature of pure CS, DES-0, DES-20 and DES-80

was summarized in Table 2 and the exhibited variation provides an
insight on the constituent's miscibility which inuences the structural
properties. It was observed that the melting temperature decreases
with addition of LiTFSI and further declines with increase in DES
content.
The reduction in the melting temperature of DES-0 compared to
pure CS reveals the possible interaction between CS and LiTFSI [19].
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.
Further decrease in melting temperature was observed upon incorporation of 20 wt.% DES in polymer electrolytes. This nding is evidence of the miscibility of DES in CS:LiTFSI matrix. The observed
decline in melting temperature was attributed to the enhancement
in structural disorderness results of the complexation, which increases the fraction of amorphous region. The atoms present in the
amorphous region are weakly bonded, thus a small amount of heat
is sufcient to overcome the weak bonding in order to melt the amorphous natured polymer matrix. Hence, a reduction in the melting
temperature will be observed as more DES content is incorporated
in the polymer electrolytes.
In view of the results, it can be noted that the melting temperature
of polymer electrolytes are reduced as more DES content is incorporated. This veries the complete miscibility of DES in CS:LiTFSI matrix
which induces structural disorderliness.

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3.4. Thermogravimetric analysis

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3.3. Differential scanning calorimetry (DSC)

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increasing plasticization of DES. Sample DES-80 obtained the highest 220

ionic conductivity owing to the presence of high concentration of mo- 221
bile Li + ions coupled with greater mobility.
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Fig. 3. Variation of tan with frequency for sample DES-80 at room temperature.

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Knowledge on the inuence of both LiTFSI and DES content on the 251
CS matrix thermal properties was evaluated by the overlay thermo- 252
gravimetric curves of pure CS, DES-0, DES-20 and DES-80 as 253
Table 2
t2:1
The melting temperature, maximum decomposition temperature and total weight loss
of pure CS, DES-0, DES-20 and DES-80.
t2:2
Sample
Temperature, T (C)
Total
t2:3
weight
Melting, Tm
t2:4
Maximum decomposition, Td
loss,
wt (%)

Fig. 2. Variation of tan with frequency for samples DES-20 (), DES-40 () and DES60 () at room temperature.

Pure CS
DES-0
DES-20
DES-80

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291.12
257.57
236.69

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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S. Ramesh et al. / Journal of Molecular Liquids xxx (2011) xxxxxx

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High conducting green polymer electrolytes were synthesized by

plasticizing the CS:LiTFSI matrix with DES. Conductivitytemperature
plot reveals the cation transport mechanism that obeys Arrhenius
rule. The maximum enhancement in the ionic conductivity was
achieved upon incorporating with 80 wt.% of DES in CS:LiTFSI matrix
with the value 4.56 10 3 S cm 1 at 50 C and activation energy of
8.22 kJ mol 1. The continuous displacements of tan peak at higher
frequency upon the increase in DES content suggest the increase in
the ionic transport mechanism. Sample DES-80 exhibits the highest
relaxation frequency with the value of log m = 6.03 indicating its
low relaxation time. The melting temperature of polymer electrolytes
decreases with the increase in DES content due to the occurrence of
complexation that suppresses the crystalline phase. 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.

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4. Conclusion

References

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represented in Fig. 4. The maximum decomposition temperature and

total weight loss being obtained from Fig. 4 have been recapitulated
in Table 2.
Based on the thermogravimetric curve of DES-0, an improvement
in both the heat-resistivity and thermal stability of pure CS was observed upon incorporation of LiTFSI. 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. Since it is heat stable,
less monomer will be detached from the complex structure, hence
lowering the total weight loss.
Thermal properties are further altered upon addition of DES in
polymer electrolytes. It can be observed that the DES plasticized polymer electrolytes exhibited weight loss starting at temperature 100 C,
which was almost 200 C lower than those experienced by nonplasticized sample as in Fig. 4.8. These reveal that the crystalline
structures of the plasticized samples were not sustained due to the
good miscibility of DES in CS:LiTFSI matrix.
The displacement of the maximum decomposition temperature of
sample DES-20 to lower temperature reveals the decline in the samples heat-resistivity. The diminishing heat-resistivity explains the
possible structural disorderness in CS matrix that leads to the existence of high amorphous fraction, having atoms that poorly coordinated. Apparently, small amount of heat is sufcient to overcome
the weak interactions between the connected atoms and hence
decomposed at lower temperature. This incorporation improves the
thermal stability of the polymer electrolytes which is evidenced by
the reduction in total weight loss.
Further increase in DES content leads to the decline in both the
heat-resistivity and thermal stability. This was associated with the
presence of greater amorphous phase in the polymer electrolytes
making it more heat sensitive. Hence, 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].
With reference to sample DES-20, the displacement of the maximum decomposition temperature to lower temperature reveals the
decline in the samples heat-resistivity. The diminishing in heatresistivity reasonably explains the possible structural disorderness
in CS matrix that leads to the existence of high amorphous fraction

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Fig. 4. Thermogravimetric curves for pure CS (), DES-0 (), DES-20 () and DES-80 (x).

which easily decomposes at lower temperature. Nevertheless this effort improves the thermal stability of the polymer electrolytes evident by the lesser total weight loss.
Further increase in DES content leads to the decline in both the
heat-resistivity and thermal stability. This was associated to the presence of greater amorphous phase in the polymer electrolytes making
it more heat sensitive. Thus, 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].

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