Conductivity and Dielectric Behavior
Conductivity and Dielectric Behavior
Conductivity and Dielectric Behavior
To cite this article: M. S. A. Rani, N. A. Dzulkurnain, A. Ahmad & N. S. Mohamed (2015) Conductivity
and Dielectric Behavior Studies of Carboxymethyl Cellulose from Kenaf Bast Fiber Incorporated with
Ammonium Acetate-BMATFSI Biopolymer Electrolytes, International Journal of Polymer Analysis and
Characterization, 20:3, 250-260, DOI: 10.1080/1023666X.2015.1013176
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International Journal of Polymer Anal. and Charact., 20: 250–260, 2015
Copyright # Taylor & Francis Group, LLC
ISSN: 1023-666X print/1563-5341 online
DOI: 10.1080/1023666X.2015.1013176
2
School of Chemistry Science and Food Technology, Faculty of Science and Technology,
Universiti Kebangsaan Malaysia, Bangi, Selangor Darul Ehsan, Malaysia
3
Centre for Foundation Studies in Science, University of Malaya, Kuala Lumpur, Malaysia
This work was undertaken to study the conductivity and dielectric behavior of a biopolymer
electrolyte based on carboxymethyl cellulose that was synthesized from kenaf fiber. Biopolymer
electrolytes comprised of various weight percentage ratios of the host polymer, ammonium acetate
salt, and butyl-trimethyl ammonium bis(trifluoromethylsulfonyl)imide ionic liquid were prepared
by the solution casting technique. The conductivity values were determined by impedance
spectroscopy. The highest conductivity found was 2.18 103 S cm1 at ambient temperature for
the film incorporated with 20 wt.% salt and 20 wt.% ionic liquid. In order to understand the
conductivity behavior, a dielectric study was carried out. The results showed that the system obeys
the Arrhenius rule and confirmed non-Debye behavior in the sample.
INTRODUCTION
Since Wright[1] and Armand et al.[2] reported the ionic conductivity of polymer-alkali metal
electrolytes, polymer electrolytes (PEs) have played an important role in solid state ionics
due to their unique properties such as ease of fabrication into thin film with large surface area
to give high energy density, the ability to accommodate a wide range of doping salt composi-
tions, good electrode-electrolyte contact, and high ionic conductivity.[3] PEs are promising
materials for the ever-growing need for high-energy-density power sources. The use of solid
polymer electrolytes can avoid problems related to liquid electrolytes such as leakage, poor
chemical stability, and reaction with electrodes. However, most of the research has used syn-
thetic polymers as hosts such as polyethylene oxide and polyvinyl alcohols; they possess such
disadvantages as high cost and not being environmentally “green.”
The use of natural polymers like chitosan,[4–6] carrageenan,[7,8] starch,[9,10] agar,[11,12] and
cellulose[13,14] is believed to be capable of solving these problems. Among these, cellulose is
an abundant and naturally occurring polymer exhibiting good mechanical properties and is also
nontoxic, renewable, ecofriendly, biodegradable, and derivatizable.[15] In its natural state,
cellulose has low conductivity, but this is expected to increase by doping with appropriate
ion-donating salts. The conductivity of cellulose may be further enhanced by chemical modifi-
cation of cellulose to form carboxymethyl cellulose. The purpose of modifying the cellulose
structure obtained from kenaf fiber is to introduce more functional groups; this indirectly
provides more active sites for charge carriers to travel, thus making the electrolyte more
conductive.
Optimizing ionic conductivity is the most important goal in the field of PEs. Plasticization is
one of the promising methods to enhance ionic conductivity. In this method, a mixture of
polymers of low molecular weight is incorporated into the host to assist in dissolution and
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dissociation of salts, reducing viscosity of the PEs and thus facilitating the movement of the
charge carriers.[16,17] In recent years, ionic liquids (ILs) have been suggested for electrolyte
applications.[18–20] ILs have attracted the attention of many researchers, especially electroche-
mists. ILs have been claimed as “green” solvents and possess good characteristics that lead to
excellent performance of electrolyte systems.[21] Their high ionic conductivity, besides the
absence of volatiles, greatly improves the safety characteristics of electrolyte systems.[22]
Additionally, the nonvolatile nature of ILs may prevent poor interfacial stability during the
reactivity between ILs and electrolytes. Studies conducted by Fernicola et al.[23] showed that
incorporation of ionic liquids in an organic electrolyte solution leads to enhancement of ionic
conductivity, besides stabilizing the lithium ions carried on the surface of the PVDF-base mem-
brane. In addition, ILs meet the requirements of plasticizing salts and offer improved thermal
and mechanical properties to polymers.[24]
The present work was carried with the objective to investigate the conductivity and dielectric
behavior of carboxymethyl cellulose (CMC)–based biopolymer electrolyte (BPE) from kenaf
fiber incorporated with ammonium acetate, NH4CH3COO, and an ionic liquid, butyl-trimethyl
ammonium bis(trifluoromethylsulfonyl)imide (BMATFSI). To the knowledge of the present
authors, there is no report of dielectric studies on salted and plasticized CMC from kenaf fiber
systems available in the literature. Therefore, investigations of the effects of salt and plasticizer
on the ionic conductivity and dielectric properties of CMC from kenaf fiber–based BPEs were
carried out. Incorporation of BMATFSI, which plays the role of charge carrier and plasticizer,
was expected to enhance the ionic conductivity of the salted system. The effect of temperature
on conductivity behavior of the biopolymer film was also investigated.
EXPERIMENTAL SECTION
Preparation of Electrolytes
CMC was obtained from raw kenaf bast (Hibiscus cannabinus) fibers. Kenaf fibers underwent
alkali treatment and a bleaching process. The significance of the alkali treatment was to
eliminate the alkali-soluble components, while the bleaching treatment was conducted to
remove the residual lignin. Cellulose that was free from lignin reacted with monochloacetic acid
252 M. S. A. RANI ET AL.
and underwent some process to produce CMC. CMC was dissolved in 40 mL of 1% acetic acid
at ambient temperature. The solution casting technique was employed to obtain films with
varied amounts of ammonium acetate, NH4CH3COO concentration (10–40 wt.%), and
BMATFSI. Complete dissolution was achieved after several hours of stirring at room tem-
perature using a magnetic stirrer. The final clear solution was then poured into separate petri
dishes and left to dry at room temperature to form highly translucent thin films. Biopolymer
electrolyte films were transferred to a desiccator for further drying prior to characterization.
Electrolyte Characterization
The impedance of the films was determined using a Solartron 1260 impedance/gain phase ana-
lyzer (Kingston on Thames, UK) for the frequency range between 10 Hz and 4 MHz. Impedance
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spectroscopy study was performed to determine the ionic conductivity of biopolymer electrolyte
films over a temperature range from 30° to 80°C. The films were cut into a suitable size
and were sandwiched between two stainless steel electrodes of diameter 2.0 cm under spring
pressure that were connected to a computer.
Figure 1 shows typical complex impedance spectra for BPE film of CMC:20 wt.%
NH4CH3COO:20 wt.% BMATFSI system at different temperatures. There is no semicircle
found in this complex impedance plot, suggesting the dominance of the resistive component
of the PEs.[25] The impedance spectra illustrate the low frequency spike, which reveals that
the conduction is mainly due to ions. Based on the work conducted by Jacob et al.,[26] it can
be concluded that the total conductivity is the result of ionic conduction in the prepared PEs.
Besides that, the inclined spikes, which are at an angle of less than 90° to the real axis, obtained
in this present work can be explained by the roughness of the electrode-electrolyte interface.[27]
FIGURE 1 Complex impedance spectra for CMC-20 wt.% NH4CH4COO-20 wt.% BMATFSI BPE at different
temperatures.
CMC FROM KENAF BAST FIBER 253
where t is the thickness of the film and A is the area of film-electrode contact. From Figure 1, it
can be observed that the bulk resistance decreases with temperature. This is attributed to the
enhancement in the number of charge carriers and their mobility with temperature.
Conductivity Study
further increase in NH4CH3COO content. The improved ionic conductivity could be attributed
to the enhancement in number of charge carriers; however, the decrement in ionic conductivity
as shown in Figure 2(a) is ascribed to the formations of neutral ion pairs, which do not
contribute toward ion conduction.[28] A comparative study by Buraidah et al.[29] reported that
the aggregation of ions impedes the movement of mobile ions, resulting in a decrease in ionic
conductivity. This system with optimum conductivity was chosen to be incorporated with an
ammonium-based ionic liquid, BMATFSI.
Figure 2(b) reveals the variation of ambient temperature conductivity with weight percent of
BMATFSI for the plasticized system. The remarkable effect of the incorporation of ionic
liquid increases the conductivity by one order of magnitude to a maximum value of 2.18
103 S cm1 at 20 wt.% of BMATFSI. Shukur et al.[30] reported that the highest conductivity
of cornstarch-doped lithium iodide plasticized with glycerol electrolyte was 9.56 104 S
cm1. The higher conductivity value obtained in this work reveals that the conductivity of
BPE can be enhanced further by incorporation of ionic liquids. Beyond this maximum value,
the conductivity decreases with an increase in weight percentage of BMATFSI. These results
FIGURE 2 Variation of room temperature conductivity with weight percentage of (a) NH4CH3COO and (b)
BMATFSI.
254 M. S. A. RANI ET AL.
are in agreement with those described in the literature.[31] The initial increase in conductivity is
attributed to BMATFSI creating more pathways for proton (Hþ) conduction. In this work,
BMATFSI is believed to act as charge carrier and also as a plasticizer, an agent to cause more
salt to be dissociated besides opening up narrow rivulets of ionic liquid-rich phases for greater
ionic transport.[32,33] As a result, the conductivity increases as the amount of ions increases.
However, the drop in conductivity with more than 20 wt.% of BMATFSI can be explained
by the displacement of the host polymer by BMATFSI molecules within the NH4CH3COO
complexes. The formation of linkages between the BMATFSI causes the salt to recrystallize,
as observed on the films, resulting in a conductivity decrement.[34] For this study, the amount
of BMATFSI was limited to 40 wt.% since biopolymer films containing more than this amount
of ionic liquid suffer from poor mechanical stability.
The variation of conductivity with temperature for samples CMC-20 wt.% NH4CH3COO
and CMC-20 wt.% NH4CH3COO-20 wt.% BMATFSI BPE is presented in Figure 3. The con-
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ductivity of both BPEs shows an increasing trend with increase in temperature, which is
ascribed to the increase of density and mobility of ions.[35]
All the points of each plot in Figure 3 lie on a straight line and the regression value is
approximately 1. The linear relationship confirms that the biopolymer system obeys the Arrhe-
nius type thermally activated process.[3] From the plot of log r versus 1000/T, the activation
energy, Ea, was calculated using the equation:
r
Ea ¼ ln kT ð2Þ
r0
where Ea is the activation energy, r is the conductivity, rο is the pre-exponential factor, k is the
Boltzmann constant, and T is the temperature.
Displayed in Figure 4 is the plot of activation energy versus concentration of NH4CH3COO
and BMATFSI. Ea is the energy required for an ion to migrate from one site to another. The
salted BPE system has an Ea value of 0.17 eV, while the plasticized BPE system has an Ea value
FIGURE 3 Temperature dependence of ionic conductivity: (a) CMC-20 wt.% NH4CH4COO and (b) CMC-20 wt.%
NH4CH4COO-20 wt.% BMATFSI.
CMC FROM KENAF BAST FIBER 255
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FIGURE 4 Activation energy vs. concentration of (a) NH4CH3COO and (b) BMATFSI.
of 0.067 eV. This trend of the Ea values suggests that BMATFSI plays an important role in
creating more pathways for charge carriers in the migration process besides increasing the
amorphous nature of the salted system, which facilitates fast ionic motion in the polymer net-
work. In addition, this result reveals that the ions in highly conducting samples require lower
energy for migration. The conductivity behavior of BPEs was further investigated by dielectric
study.
Dielectric Study
Dielectric relaxation study is a vital tool to elucidate the relaxation of dipoles in polymer
electrolytes. In general, polymers show several kinds of dielectric absorption associated
with various kinds of molecular relaxation. Besides, it provides important insights into the
polarization effect at the electrode/electrolyte interface, thus aiding our understanding about
conductivity trends.[36] The complex dielectric constant, er, and dielectric loss, ei, were
calculated as follows:
Zi
er ðx Þ ¼ ð3Þ
xC0 Zr 2 þ Zi 2
Zr
ei ð x Þ ¼ ð4Þ
xC0 Zr 2 þ Zi 2
where Cο ¼ eοA/t (eο is permittivity of free space), A is electrode-electrolyte contact area, t is the
thickness of the electrolyte, x ¼ 2πf (f is frequency), Zi is the imaginary part of complex
permittivity, and Zris the real part of complex permittivity.
Graphs of log er–log x for the sample with the highest ionic conductivity of the CMC-
NH4CH3COO-BMATFSI system are depicted in Figure 5. The incorporation of the ionic liquid
BMATFSI, which acts as plasticizer, into CMC-NH4CH3COO complexes is expected to
256 M. S. A. RANI ET AL.
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FIGURE 5 (a) Dielectric constant and (b) dielectric loss for the sample with 20 wt.% of BMATFSI at different
temperatures.
increase the degree of salt dissociation and enhance the number of free ions. Therefore, the
increase in conductivity is due to the association of ions or decrease in mobility of the
ions.[37] In Figure 5, it can be observed that the variation in er and ei with angular frequency
could be attributed to the formation of the space charge region at the electrode-electrolyte inter-
face. This confirms non-Debye dependence, implying that the charge region with respect to the
frequency is explained in terms of ion diffusion.[38,39] There were no appreciable relaxation
peaks observed in the frequency range employed in this work.
The dielectric plot in Figure 5(a) illustrates higher values of the dielectric constant, er, in the
low frequency region. This phenomenon can be explained by the presence of blocking electro-
des as the transfer of mobile ions in the external circuit could not be permitted, resulting in ion
accumulation near the electrode, and the bulk polarization effect in the materials is produced.[40]
Furthermore, it can be inferred that the enhancement of frequency caused the dipoles to be
unable to keep in pace with the fast changing field. This would lead to a drop in er values with
increasing frequency.[41] Meanwhile, the dielectric loss, ei, becomes very large at lower fre-
quencies, as depicted in Figure 5(b), which can be explained by free charge motion that builds
up at the interface between the materials and the electrodes. Besides that, the ei trend shows the
appearance of a dominant dielectric relaxation peak, whose maximum shifts gradually with the
increment of frequency with increasing temperature. This high frequency b-relaxation peak may
be attributed to the side group dipoles.[40]
Both the dielectric constant, er, and dielectric loss, ei, increase with temperature, and this is
due to the migration polarization of the mobile ions.[42] This phenomenon explains the fact that
heat or temperature increases the degree of salt dissociation and re-dissociation of ion aggre-
gates, resulting in enhancement of conductivity due to higher content of free ions or charge
carrier density. On the other hand, the value of er and ei decreases with increasing frequency
due to the high periodic reversal of the applied field. Therefore, there was no time for charge
to build up at the interface. The polarization due to the charge accumulation decreases, leading
to the drop in the values of er and ei.[38,43] A further investigation of the dielectric behavior can
be more successfully achieved using a modulus study that suppresses the effect of electrode
polarization.[44]
CMC FROM KENAF BAST FIBER 257
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FIGURE 6 Frequency and temperature dependence of imaginary spectra of Mi for the highest conducting sample.
Modulus Study
CONCLUSIONS
FUNDING
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Sincere gratitude goes to the Ministry of Higher Education, Malaysia, for the scholarship under
MyBrain15 given to Mohd Saiful Asmal Rani. Financial support from the University of Malaya
(research grant RG255-13AFR and PG092-2014A) is also gratefully acknowledged.
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