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Article

High performing Bio-based ionic liquid crystal electrolytes for supercapacitors

Renjith Sasi, Sudha Janardhanan Devaki, and Sujatha Sarojam
ACS Sustainable Chem. Eng., Just Accepted Manuscript DOI: 10.1021/
acssuschemeng.6b00585 Publication Date (Web): 16 May 2016
Downloaded from http://pubs.acs.org on May 19, 2016

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High performing Bio-based ionic liquid crystal

electrolytes for supercapacitors
Renjith Sasia, Sujatha Sarojamb, and Sudha J Devakia*
* E-mail:sudhajd2001@yahoo.co.in
a

Chemical Sciences and Technology Division, CSIR-National Institute for Interdisciplinary

Science and Technology (CSIR-NIIST), Thiruvananthapuram, 695019, India.
b

Battery Division, Vikram Sarabhai Space Centre (VSSC), Thiruvananthapuram, 695022,

India.

ABSTRACT: Production and storage of energy in a highly efficient and environmentally

sustainable way is the demand of current century to meet the growing global energy requirement.
Design and development of novel materials and processes that allow precise control over the
electrochemical behavior and conductivity of electrolytes is necessary for acquiring such targets.
Development of ionic liquid crystals with ordered domains endowed with enhanced ionic
conductivity from renewable resources is receiving much interest in this respect. In this paper,
we report a unique strategy for the preparation and utilization of ionic liquid crystalline
electrolyte derived from a renewable resource: cashew nut shell liquid; an abundantly available

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waste by-product from cashew industry. We have prepared imidazolium-based ionic liquid
crystal (PMIMP) from cardanol and studied its structure and liquid crystalline phase formation
by various techniques. The symmetrical supercapacitor fabricated with mesoporous carbon
electrodes employing PMIMP as electrolyte measured a specific capacitance of 131.43 F/g at a
current density of 0.37 A/g with excellent cycle stability and 80 % capacitance retention after
2000 cycles. All these excellent properties of the prepared ionic liquid crystalline electrolyte
suggest its application as an efficient, environmentally friendly and low-cost electrolyte for
energy storage devices.

KEYWORDS: Bio-based ionic liquid crystals, self-assembly, electrolyte, rheology,

supercapacitors, energy storage

INTRODUCTION

Ionic liquid crystals (ILCs) form a versatile class of compounds combining the intriguing
properties of ionic liquids as well as liquid crystals.1 They carry labile ionic centres arranged in a
quasi-ordered manner giving one-dimensional stimuli-responsive conductivity suitable for
conduction, transport and storage of electric charge. ILCs consists of rigid aromatic cores for
long range ordering, ionic centres for charge and alkyl chains for mobility modulations.25 The
versatility in design, easy exchangeability of ions, tunable charge transport properties, lower
toxicity and vapour pressure makes them hot cakes in the new age energy research.69 Unlike
Ionic liquids, ILCs can form conducting films with suitable binders making them wonderful
candidates to be used as solid electrolytes in energy devices which improve connectivity and
avoids the leakage and pollution. As the global concern for green research rises day by day, the
scientific world is in search of alternate eco-friendly resources for energy production and
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storage.10,11Environmentally benign materials for energy harnessing are hot topics nowadays as
the world suffers severely from environmental pollution, global warming, etc. mainly due to the
improper selection and usage of energy resources. Minimization of waste disposal, re-use of
materials and converting waste materials into useful products are three imperative goals put
forwarded by environmentalists to safeguard our mother nature. Exponential material
consumption of modern society had resulted in the accumulation of huge tonnes of wastes in the
environment whose disposition itself costs a tremendous amount of manpower and energy.
Conversion of troublesome wastes into economic and high-throughput energy currencies seems
an intelligent move to conserve the environment and solve the energy crisis.Steps have already
taken to convert industrial wastes and by-products into useful articles and energy resources for
making our planet clean.1214Waste derived carbon materials are widely employedfor various
energy storage devices as efficient and profitable electrode materialsrecently.1519The global
scientific community is in search for alternate, low-cost, eco-friendly technology for the
production of electrical energy.20
Storage of electrical energy is also a crucial technological area which needs intense research.
Electrolytic capacitors and batteries offer a sustainable way for stable and consistent energy
storage. Batteries involving Li-ion or metal/metal hydride couple provide energy discharge with
high energy density. Complimentary to them electrolytic capacitors are capable of discharging
with high power density. Supercapacitors having properties intermediate to batteries and
electrolytic capacitors displays faster charge- discharge rates, higher cycle lives, simple and
flexible designs which make them prospective candidates in electronic devices, medical
appliances, military instruments and in hybrid transportation systems.21 The device performance
can be tuned by improving its energy density through the design of new electrode materials, new

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electrolytes, and new electrochemical concepts.22,23Currently both organic and aqueous

electrolytes were employed for extracting high performance from carbon-based supercapacitors.
Energy and power densities of supercapacitors were limited by the electrochemical window of
the electrolytes used for the charge transport. Aqueous electrolytes have lower electrochemical
windows in comparison with organic electrolytes but they are less toxic in nature making them a
primary choice. Electrolyte depletion is another important hindering factor of conventional
electrolytes. The ILCs have the good electrochemical window and appreciable conductivity to be
applicable in electrochemical energy devices as efficient electrolytes.24,25 Ionic liquids and ionic
liquid crystals with combined effects of organic and aqueous electrolytes seem to be a better
replacement for conventional electrolytes.2629 Bio-based ionic liquid crystals are attracting
attention nowadays, as they provide a healthy alternative for petroleum-based materials by
performing their respective function with less harm to the environment.30
Cashew industry has been one of the prime industries in Kerala for a long time. Export of
cashew kernels is earning a considerable share of Keralas annual income. In Kerala, there are a
vast number of cashew factories processing and packaging cashew nuts in large scale. Earlier the
nutshells have been burnt to ashes without knowing their value. Later it was discovered that the
extract of cashew nutshell, known as cashew nut shell liquid (CNSL) is a rich source of a variety
of long alkylated phenols particularly 3-pentadecenyl phenol (cardanol).31,32 A library of
cardanol derived functional materials have been reported by our group as dopants, templates,
sensors and so on.3335In this paper, we are presenting a new class of ionic liquid crystal which is
derived from cardanol (3-Pentadecenyl phenol) to be used as an electrolyte for energy storage
devices. It possesses unique bent-core design for facilitating both liquid crystalline ordering and
excellent conductivity. The well characterized ionic liquid crystal found to be having a good

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electrochemical window and ionic conductivity (~40 mS/cm at 0.50 M in acetonitrile) for
displaying excellent capacitive performance. Symmetric supercapacitors employing mesoporous
carbon as the electrode material were fabricated with 0.50 M solution of Ionic liquid crystal in
acetonitrile as electrolytesto check the supercapacitor performance. It exhibits a high specific
capacitance of 131.43 F/g with excellent cycle stability at a current density of 0.37 A/g.

RESULTS AND DISCUSSION

Scheme 1.Synthesis of PMIMP.

We have distilled CNSL under vacuum at 200 C to obtain cardanol which was further reduced
to 3-pentadecylphenol (3-PDP). O-alkylation of 3-PDP followed by quaternization with 1-methyl
imidazole to yield a class of bio-based ionic liquid crystal with distinct bent-core geometry
(Scheme. 1). Formation of targeted compounds was confirmed by various spectroscopic
techniques such as FT-IR,

HNMR and HRMS. Details of synthetic procedures and

characterization methods are given in supporting information.

1

HNMR spectroscopic analysis gave characteristic spectra showing the chemical shift ()

values confirming the formation of targeted compound. Peaks around the chemical shift values
of 8.44 and 7.25 ppm corresponds to the aromatic protons in the imidazolium cation. Resonance
of aromatic protons in the benzene ring gave rise to characteristic peaks around 7.16, 6.76 and
6.67 ppm. Sharp singlet observed at 3.85 ppm attributed to the equivalent protons present in the
methyl group attached to the imidazolium ring. Methylene groups near to the aromatic rings and

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hetero atoms gave peaks at 4.22, 3.95, 2.55 and 2.05 ppm respectively. Remaining methylene
groups resonated to give signals in between 1.25 and 1.81 ppm. Terminal methyl group of
aliphatic chain gave characteristic triplet at 0.88 ppm. 1H NMR spectrum of PMIMP is given in
the Figure S1. In the FT-IR spectrum of PMIMP, The multiple IR peaks in the range of 28003000 cm-1 are due to the symmetric and asymmetric C-H stretching vibrations of the alkyl chains
whereas the multiplets in the range of 3000-3200 cm-1 are attributed to the C-H vibrational
modes of aromatic rings. The peaks in the range of 1600-1585 cm-1 are assigned to C-C
stretching and C-N bending vibrations. The peak at 1455 cm-1 is corresponding to C-H alkyl
deformation while C-N stretching vibrations are observed at a frequency of 1189 cm-1. The sharp
peak at 1158 cm-1 corresponds to the C-O-C stretching of alkyl aryl ether. P-F stretching
vibrations of PF6 anion produce a characteristic peak around 820 cm-1.36 FT-IR spectra of
BBPDB and PMIMP are given in the Figure S2. Molecular geometry optimization by B3LYP
using 6-31g* basis set showed that PMIMP has unique bent-core structural design containing
long aliphatic chain, aromatic cores and ionic centres enabling self-assembly via layer by layer
inter-digitation, - stacking and electrostatic interactions (Figure S3). Such non-covalent
interactions are prone to re-alignment on introducing suitable external stimuli such as
temperature, solvent, electric field, etc. which gave rise to liquid crystalline phases.
Thermotropic phase transitions
Thermotropic phase transitions were studied by DSC analysis in conjugation with a hot stage
equipped PLM. In the heating ramp, PMIMP displayed a transition from crystalline phase to
columnar phase at 90.00 C and the isotropic phase at 118.00 C with enthalpy changes 7.89 J/g
and 34.82 J/g respectively (Figure 1a). On cooling from the isotropic melt, PMIMP developed
columnar phase around 96.90 C and is converted into Smectic F phase at around 69.50 C on

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further cooling. It generated crystalline phase around 61.00C also, and the corresponding
thermodynamic variations are listed in Table.S1. More mobile charge carriers in the quasiordered liquid crystalline phase improved the conductivity of the system at the onset of
crystalline to columnar transition. PMIMP showed a low conductivity of 6.50 10-8 S/cm at
room temperature, and it increased gradually with temperature and above 90.00 C; there
occurred an exponential increment in conductivity due to the formation of columnar phase. It
further increased to 2010-3 S/cm at 115 C, at the onset of Columnar- Isotropic phase change.
After melting, conductivity remains almost constant with increase in temperature. Conductivity
enhancements observed were fitted extremely well with the thermotropic phase changes under
DSC as displayed in Figure 1a. Thermotropic liquid crystalline phase formation was followed by
polarized light microscopic analysis also. Images were taken while cooling the ionic liquid
crystal from isotropic phase at 120 C at a rate of 5 C/min. During cooling, the randomly aligned
ionic liquid crystal molecules were brought to supramolecular organized liquid crystalline phase
by various non-covalent interactions such as ionic, electrostatic layer by layer assembling and
other van der Waals interactions leading to the formation of liquid crystalline phases of different
orders which depends on the extent of the tilt of molecular alignment from the principle director
(the plane perpendicular to the aligned molecular layers).37 DSC displayed an exothermic peak
around 97 C, suggesting that PMIMP molecules self-assembled to give columnar mesophase as
confirmed by observation under PLM. Characteristic focal conic domains of columnar phase
obtained at 97 C are shown in Figure 1c. On further cooling from columnar phase, the entropy
of the system again decreased which was compensated by the increment in molecular ordering to
generate higher degree of order and simultaneous tilt of the molecular chains toform another type
of focal conic domains with stripes. This columnar-Smectic liquid crystalline phase transition

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was accompanied by the enhancement of birefringence with the simultaneous appearance of

circular stripes along the focal conic domains. The typical mosaic texture of Smectic mesophase
was observed at 69.50 C as depicted in Figure 1d. This homeotropic mosaic texture together
with planar circularly striped cone texture is typical for liquid crystalline Smectic F phases.38
Temperature dependent rheological studies revealed the variation in viscoelastic behavior at
the onset of thermotropic phase transition.39 Above 120 C, when PMIMP melt, a sheardependent viscoelastic profile showing non-Newtonian fluidic behavior with elastic prominence
in the lower shear regime was observed. On increasing the shear strain, both storage (G) and
loss moduli (G) decreases and G overtook G at a shear strain of 4.23 % to obtain a viscous
phase. High G value displayed by PMIMP even in the isotropic phase is attributed to the
combined effect of layer-by-layer stacking of alkyl chains and strong ionic interaction between
the imidazolium cation and counter anion. On cooling from the melt, the values of G and G
increased exponentially and become independent of shear rate. At a shear strain of 20 %, G rose
from 98.20 Pa to 12.01 kPa on cooling from isotropic melt to columnar phase at 90.00 C.
Variation of viscoelastic moduli and viscosity with shear strain at isotropic (130.00 C) and
columnar (90.00 C) phases is given in Figure S4. Temperature ramp at an angular frequency of
10 Hz from 130.00 C where isotropic phase prevails to 40.00 C illustrated the clear variation of
viscoelastic properties on the thermotropic phase transition (Figure 1b). Storage modulus
increased exponentially on cooling from 130.00 C before attaining a plateau showing the
establishment of molecular self-assembly.40 As it cooled further intermolecular interactions
reinforced to generate columnar phase observed as a discontinuity in the viscoelastic profile.
Sudden enhancement of G and complex viscosity around 53.00 C is attributed to the formation
of well-packed crystalline phase. These observations are in good agreement with DSC analysis.

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Figure 1.a) DSC heating and cooling scans of PMIMP showing thermotropic behavior and
corresponding variation in conductivity and b) thermotropic variation in viscoelastic moduli of
PMIMP. PLM images of c) focal conic domains of columnar phase and d) Smectic F phase
formed.
PMIMP displayed highly ordered crystalline structure in the room temperature wide angle Xray diffraction (WAXD) due to strong ionic interactions pertained between charged counterparts
and layer by layer inter-digitation of long alkyl chains (Figure 2a). On heating, it is converted
into an amorphous profile without any characteristic peaks at 120C showing the complete
conversion into the isotropic state. When cooled from the melt, it generated a quasi-ordered
profile with the lesser number of reflections at 90.00 C corresponding to the columnar
mesophase. The strong peaks in the WAXD profile of the columnar phase with d-spacings 6.43
and 4.23 correspond to the core stacking of the imidazolium cations. It regains its original

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crystalline pattern when cooled down to room temperature suggesting strong thermo-responsive
behavior of PMIMP. The SAXS pattern of PMIMP at 90 C (Figure 2b) displayed peaks with
reversible d-spacing ratio of 1: 3: 2 revealed the high degree of ordering present in the
columnar phase.41A d-spacing of 70 corresponds to (100) peak corresponds to which is more
than double the molecular length suggests that columnar phase is formed predominantly via the
ionic interaction between PMIMP molecules. Optimization of molecular geometry of PMIMP by
Gaussian 09 method using 6-31g* basis set further confirms that the d-spacings correspond to the
molecular ordering pertaining in the mesophase.
Effect of Thermotropic phase transition on electrochemical properties:
As the formation of thermotropic columnar mesophase improves the conductivity of the
system, the electrochemical properties which heavily rely on the charge carrier density will also
show significant enhancement. Electrochemical behaviors of the material in response to
thermotropic phase transitions were monitored by using a typical test cell of the configuration
ITO/PMIMP/ITO. Cyclic Voltammetry (CV) traces show rectangular shaped electrochemical
window in the region of 1.00 to 2.50 V suggests the ability of the material to store charge
effectively (FigureS5a). When the CV analysis was done at 90.00 C, an enhancement in current
occurred and the area under the CV corresponding to the charge stored in the system also
increased. Galvanostatic charge-discharge studies of the symmetric test cell confirmed the effect
of thermotropic phase transition on the capacitive behavior of the material as the discharge time
increased considerably in the liquid crystalline phase (Figure S5b). The test cell retained its
capacitive behavior even after 100 charge-discharge cycles as displayed by the symmetric
charge-discharge profiles in Figure S5c. This observation further suggests the improvement of
capacitive behavior. Impedance analysis of the cell at room temperature and 90.00 C further

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displayed the influence of mesophase formation on charge conduction. Nyquist plot of PMIMP
test cell gave typical semi-circular arc due to ionic conduction at the high frequency regime and
an inclined Warburg line at the low frequency regime attributed to the diffusion of charge
carriers (Figure S5d). Charge transfer resistance (Rct) of PMIMP obtained by extrapolating
semicircle arc to real axis decreased from 75.60 k (RT) to 28.30 k at 90.00 C vividly
substantiating the improvement of charge conduction in the mesophase. Good electrochemical
window and charge-discharge stability of the material suggest its applicability in solid state
energy storage devices. Also, thermotropic enhancement of capacitive behavior is interesting as
it will be suitable for high temperature molecular electronics.

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Figure 2.a) WAXD patterns of PMIMP at different thermotropic conditions and b) SAXS
pattern of columnar LC phase of PMIMP. c) Optimized geometry of PMIMP showing molecular
dimensions.
Lyotropic phase formation on electrochemical properties
The most important pre-requisites for material to be used as electrolytes are good ionic
conductivity and extended electrochemical window.42PMIMP exhibited good ionic conductivity
in solutions prepared in acetonitrile, a widely used solvent for electrochemical analyses.
Concentration-dependent ionic conductivity measurements of the PMIMP solutions were carried
out in combination with PLM analyses to study the effect of lyotropic phase formation on ionic
conduction. At concentrations lower than 0.10 M, no definite birefringence was observed, and
the conductivity of the solution was found to be in the range of 3.00-6.00 mS/cm. On increasing
the concentration Nematic phase with higher conductivity of 19.40mS/cm was obtained at a
concentration of 0.30 M. Conductivity further increased with concentration as columnar domains
of Sm A phase formed around 0.40 M (33.10 mS/cm)(Figure 3c). As the concentration exceeds
0.60 M, ionic conductivity began to decrease since the extended molecular association of ionic
liquid crystals resulted in the formation of higher ordered Smectic C phase (Figure 3d) and
finally gel networks. Maximum conductivity of 40.30 mS/cm was observed for a concentration
of 0.50 M. The conductivity of the electrolyte solutions depends not only on the concentration of
charge carriers but also on the viscosity of the solution. Shear dependent viscosity analysis of the
solutions displayed that viscosities of solutions were increased with concentration. On moving to
Nematic to columnar phase there occurs not much variation in viscosity but gel network found to
have higher viscosity. Variation of viscosity, as well as ionic conductivity with concentration is
given in Figure S6.

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Figure 3. Lyotropic phases formed by MIMP: AFM images of a) Nematic batonnet phase, b)
columnar phase, PLM images of c)Smectic A phase, and d) Smectic C phase.
Lyotropic ordering vividly reflected in the texture and birefringence of the film cast from
respective solutions. PMIMP film cast from solution with Nematic concentration, displayed
randomly oriented mesogens with batonnet rod-like morphology as observed under AFM (Figure
3a). Uniformly oriented Nematic mesogens possess an average height of 20.00 nm (Figure S7a
and S7b).On increasing the concentration, the mesogens were self-assembled to generate
Smectic phase with clear domain boundaries (Figure 3b).Height profile of the conical domains
showed a significant enhancement to ~150.00 nm confirming the molecular association. (Figure
S7c and S7d)
Electrolyte for Symmetric supercapacitors

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Electrolytes are one of the major components of supercapacitors whose performance will
govern the overall efficiency of the device. Even though the charge carrier density is very high
for the crystalline phase, the negligible mobility of carriers owing to the highly ordered
crystalline packing hinders the charge transport and thereby device performance. In comparison
with randomly oriented charge carriers of liquid electrolytes, ordered array of charge carriers
present in liquid crystalline electrolytes seems to deliver exceptional device performance.
Besides, they are having high carrier density and lower tendency to flow which will redeem the
possibility of environmental pollution by electrolyte leakage. In the liquid crystalline phase selfassembly of ionic molecules result in the formation of ion conducting channels with high
conductivity which will be the suitable one to act as electrolyte for supercapacitors as it will
facilitate better charge storage and transport. So, 0.50 M solution of PMIMP in acetonitrile
having excellent conductivity and low viscosity was selected as the electrolyte for fabricating
electrochemical

supercapacitors.

Symmetric

super

capacitors

were

fabricated

using

commercially available mesoporous carbon with a specific surface area of 1732.74 m2/g, as the
electrode material. The electrode material is having an average pore width of 20.16 , which was
estimated by Brunauer-Emmett-Teller (BET) method. Average pore diameter of the electrode
material is estimated by Barrett-Joyner-Halenda (BJH) method as 27.49 . Typical BET linear
isotherm and pore volume distribution of mesoporous carbon electrode material are given in the
supporting information (Figure S8). AFM analysis of the electrode material also confirmed the
existence of fine pores for facilitating adsorption of charge carriers for yielding better chargedischarge properties (Figure S9). The performances of the devices were evaluated using
Electrochemical Impedance Spectroscopy, Cyclic Voltammetry, and galvanostatic chargedischarge studies. Nyquist impedance plots of the device gave characteristic semicircle arc in the

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higher frequency regime and steeply inclining Warburg line in the lower frequencies (Figure 4a).
Bulk (Rb) and charge transfer resistances (Rct) of the device were calculated from the intercepts
of the semicircles with real axis as 3.60 (Rb) and 1.90 (Rct). Impedance analysis can also be
used to calculate knee frequency (fknee) and response time of the device, two critical parameters
highlighting the rate capability of supercapacitors.43Enhancement of fknee, the frequency at which
the capacitive behavior rapidly changes to resistive behavior implies the fast switching at the
electrode-electrolyte interface. The prepared supercapacitor has a high fknee of 251.00 Hz
showing tremendous capacitive behavior. Response time () of the supercapacitors which
quantifies their rate performance can be calculated from the Bode impedance plots (Figure 4b).
is the reciprocal of the response frequency (fres), the frequency at which the real and imaginary
components of impedance coincides or the components are separated by a phase angle of 45.00 .
As expected, PMIMP based supercapacitor has a low response time of 13.20 s confirming fast
charge transfer at the electrode-electrolyte interface.

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Figure 4a) Nyquist and b) Bode impedance plots of PMIMP based supercapacitors.

Cyclic voltametric analysis of the coin cell supercapacitor containing PMIMP electrolyte
displayed nearly rectangular shaped window devoid of any redox peaks within a potential range
of 1.00-2.50 V when cycled at a scan rate of 10.00 mV/s shows exquisite capacitive behavior

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(Figure 5a). On increasing the scan rate, the rectangular shape of the potential window remains
the same suggests that the charge transport is taking place at high rates. High rate performance is
one of the most desirable properties for supercapacitors.

Figure 5a) Rectangular CV curve of the super capacitor containing PMIMP electrolyte at
different scan rates, b) galvanostatic charge-discharge profiles of the device at various current
densities.
Galvanostatic charge-discharge studies at the constant current were performed to calculate the
specific capacitance of the device. Symmetrical charging and discharging profiles displayed a

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high degree of reversibility and better storage capability (Figure 5b). The specific capacitance
(Cs) of the devices were calculated from the discharge profile using the equation22,

 =

4

Where I is the current applied, m is the active mass of the device and V/t is the slope of the
linear part of the discharge profile excluding the initial IR drop. PMIMP based supercapacitors
drew much higher capacities of 131.43 F/g at a current density of 0.37 A/g due to higher
conduction at the electrode-electrolyte interface. Normally supercapacitors with mesoporous
carbon based electrodes deliver capacities in the vicinity of 100.00 F/g. As per literature reports,
different combinations of electrolytes have explored for extracting better capacitive performance
with mesoporous carbon electrodes. In comparison with them PMIMP based electrolyte gave
better specific capacitance. Low cost and eco-friendly nature are other advantages. Comparison
of capacitive behavior of different electrolyte systems used in combination with mesoporous
carbon electrodes and PMIMP is illustrated as Table 1.

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Carbon
CMK-3A

44
45

Banana fibre
carbon
46
OMC-600
47
Waste particle
board carbon
48
OMC
49
50

Tri-OMC

Lignin based
OMC-CO2
activated
28
Activated carbon
MTI carbon

Condition
1 mHz, single
electrode
0.50 A/g

Electrolyte
Nafion

Capacitance
132.00 F/g

1.00 M Na2SO4

74.00 F/g
105.00 F/g
119.00 F/g

5.00 mV/s

6.00 M KOH
1.00 M TEMABF4/PC
6.00 M KOH/1 M
H2SO4
1.00 M TEMABF4/PC
6 M KOH

0.50 A/g
0.18 A/g

PYR14TFSI in BuCN
0.50 M PMIMP in can

125.00 F/g
134.43 F/g

0.70 A/g
0.05 A/g
5.00 mV/s
5.00 mV/s

36.00 F/g
112.00 F/g
102.00 F/g

Table 1 Comparison of specific capacitance of PMIMP electrolyte with reported electrolytes.

Energy density (in Wh/kg) and power densities (in W/kg) of the devices were also calculated
from discharge profile using the equations given below22
 =


2 . 3600

 =

Where C is capacitance, V is the voltage range excluding IR drop, m is the active mass in kg,
and t is the discharge time in hours. 33.79 Wh/kg and 1032.98 W/kg are the energy and power
densities of the supercapacitor containing bio-based ionic liquid crystal solution as the electrolyte
when charged at a constant load current of 0.37 A/g. High energy and power densities obtained
for mesoporous carbon based supercapacitor powered by bio waste-derived electrolyte hold the
key for future energy storage systems. In addition to gravimetric capacitance, the areal

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capacitance of the supercapacitor was also measured. Comparatively high areal capacitance of
1.02 F/cm2 was obtained for a constant current loading of 2.90 mA/cm2.
Effect of constant load current on the capacitive performances of super capacitors was
monitored by varying the current densities from 0.18 A/g to 1.80 A/g (Figure 5b). Specific
capacity dropped from 134.73 F/g to 118.29 F/g on increasing the constant load current density
from 0.18 A/g to 1.80 A/g. Variation of specific capacitance with current density is illustrated in
Figure S10. It was justified by the enhancement of ESR values clearly visible from the IR drops
of discharge profiles on increasing load current which will reduce the power density of the
system significantly at higher current densities. Cycling stability studies were carried out at a
load current of 0.37 A/g to check the retention of capacities with time. PMIMP based super
capacitors displayed more than 80.00 % capacity retention even after 2000 cycles. The variation
of gravimetric and areal specific capacitance of the device with cycling is depicted in Figure 6
and typical charge-discharge profiles of first ten cycles are given in inset.

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Figure 6.Cycling stability of PMIMP based supercapacitor. First ten cycles are given in inset.

Lowering of capacitance with cycling is attributed to the enhancement of electrolyte and

charge transfer resistance on prolonged cycling. This was clearly illustrated by the impedance
analysis of the device after cycling. Rb and Rct values increased to7.26 and 2.56 respectively
which will hinder the smooth transfer of charge carriers. Cyclic voltametric profile also
displayed lowering of current conduction and slight departure from rectangular profile owing to
the increased charge transfer resistance. CV and impedance profiles of the device before and
after cycling are compared in Figure S11. Variation of energy density of the device with power
density on varying the current density is illustrated by typical Ragone plot as in FigureS12. It
shows the characteristic profile of a supercapacitor with a maximum energy density of
38.29Wh/kg corresponding to a low power density of 617.89 W/kg at a current density of 0.18
A/g. Maximum power density of 3582.53 W/kg was observed at a current density of 1.80 A/g
with a lower energy density of 17.11 Wh/kg.

CONCLUSION

A bio-based ionic liquid crystal was prepared by modifying cardanol derived from CNSL, a
waste bye-product from cashew industry. Thermotropic and lyotropic phase analyses of PMIMP
displayed the existence of typical Columnar and Smectic mesophases. Symmetric super
capacitors were prepared using mesoporous carbon based electrodes and the developed ILCs as
electrolytes. PMIMP based super capacitor showed a maximum specific capacitance of 134.73
F/g, high energy density of 38.29 Wh/kg and an impressive power density of 3582.53 W/kg. It
also gives high rate performance with lower charge transfer resistance (1.90 ) and a very small

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response time (13.20s). This strategy of utilization of an industrial waste derived soft liquid
crystalline material as an efficient electrolyte for energy storage systems may expect to add
another gold coin to the field of energy while avoiding environmental issues for a better
sustainable society.
ASSOCIATED CONTENT
Supporting Information. Experimental procedures, characterization methods,

HNMR

spectrum, FT-IR spectrum, Optimized geometry, DSC parameters, Rheological profiles,

electrochemical characterizations of solid test cell, AFM images, concentration dependent
viscosity and conductivity variation, BET profiles of electrode material and Ragone plot. This
material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author
* E-mail:sudhajd2001@yahoo.co.in
Author Contributions
All authors have given approval to the final version of the manuscript.

ACKNOWLEDGMENT
We thank CSIR and UGC for the financial support. We would like to thank Dr. A.
Ajayaghosh, director, CSIR-NIIST, Trivandrum for his constant encouragement and
support. We are thankful to Mr. Aswin Maheswar for AFM analysis. We are also
thankful for the financial support from CSIR network project MULTIFUN (CSC0101).

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High performing Bio-based ionic liquid crystal

electrolytes for supercapacitors
Renjith Sasia, Sujatha Sarojamb, and Sudha J Devakia*
a

Chemical Sciences and Technology Division, CSIR-National Institute for Interdisciplinary

Science and Technology (CSIR-NIIST), Thiruvananthapuram, 695019, India.
b

Battery Division, Vikram Sarabhai Space Centre (VSSC), Thiruvananthapuram, 695022,

India.

Renewable resource based low cost eco-friendly ionic liquid crystals as power
electrolytes for efficient supercapacitors

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Ionic liquid crystal as electrolyte for supercapacitors

166x111mm (150 x 150 DPI)

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