ELAN & NVISION 2018 1

Mayank Saraswat
Sonochemical Synthesis of Cellulose and PANi
based Nanocomposites for Supercapacitors
Department of Chemical Engineering
National Institute of Technology,Warangal.

electrodes

Abstract (With the everyday "flying development" in the economy ,it has become difficult to meet the
increasing energy demand through clean and efficient energy storage devices.The energy storage devices
like Li-ion batteries,fuel cells and supercapacitors can prove as"magnificient stars" in this field.So,Here in
this paper, ultrasound assisted synthesis of electrodes for one such device ,'Supercapacitor' has been
discussed.Cellulose,abundant in nature ,can be attractively doped with PANi(poly aniline) as active material
for high performance supercapacitors.Polyaniline(PANi),a conducting polymer can be used to provide high
specific capacitance,high flexibility in combination with high strengths resulting due to cellulose nanofibrils
synthesisable at low costs.The following paper also discusses the easy synthesis of Cellulose Nanofibres
(from cotton fibres) and PANi using sonochemical methods and the fabrication of electrode from this
composite to be put into use in supercapacitors.The paper concludes with the discussion of the advantages
of cellulose-PANi based supercapacitors over classical energy storage devices with either low specific
capacitance or low energy density besides their low natural abundance,high costs and low conductivity and
how this easy composite can be further doped with other conducting polymers to obtain still higher values
of specific capacitance upto 560 F g-1and more.
Index Terms—Supercapacitors , Sonochemical Synthesis,Polyaniline,Cellulose

low-cost, lightweight, environmentally friendly,

I. INTRODUCTION1
The unprecedented advancements in portable
electronic systems during the past two decades
has turned the attention
of researchers to developing equally versatile
energystorage
devices such as batteries, supercapacitors, or fuel
cells.[1,2] Of these, supercapacitors have
important features that bridge the gap between
batteries and conventional capacitors in terms of
energy density, power density, and cycle life.
Continuous development of novel electrode
materials and new device architectures has
nourished progress in building better energy
storage devices.
Simultaneously, the next-generation smart
electronics industry has high requirements for
sustainability, and extraordinary achievements are
going to be needed regarding the development of
high-performance supercapacitors and batteries.
2.Ultrasound Assisted Synthesis(Sonochemical
Synthesis)-
Using high power ultrasound offered a potentially
facile and versatile tool for surface
functionalization/oxidation of nanotubes, lowering
the reaction time(Iike, a conventional reaction
time of 4hours can be reduced to just 20 minutes
if we employ ultrasound) and overall energy
requirements as well. The major effects arise from
acoustic cavitation, where the formation, growth
and implosion of bubbles in the liquid generates
reactive intermediates such as hydroxyl radicals as
a result of solvent breakdown due to high
pressures (∼1000 bar) and temperatures (∼5000

1
K). Shock waves and microjets also occur which
could overcome the interactions causing
aggregation to disperse the Cellulose Nanofibres
and also generate deformities on the nanofibres
surfaces leading to functional groups being formed
on their surfaces. These features have been shown
to play a crucial role in surface functionalization.
[1-2]

2.1 ACOUSTIC CAVITATION- Fig 2.Ultrasonic Probe Sonicator (~20kHz)

Liquids exposed to high-intensity ultrasound can
undergo acoustic cavitation. This phenomenon can
typically be seen as a cloud of bubbles forming in
the vicinity of the ultrasonic source (e.g.,
ultrasonic horn) and heard as an intense hissing
noise. Cavitation is the formation of low-pressure
voids (a.k.a., vacuum bubbles or cavities) in the
liquid, which grow, briefly oscillate and then
asymmetrically implode with great intensity.
2.1.1 Physical and chemical effects of Acoustic
cavitation-
Violent bubble collapse during cavitation causes
extreme local temperatures (up to ~ 5,000 oC),
heating/cooling rates (up to ~ 10 billion oC/sec)
and pressures (up to ~ 1,000 atm), producing free
radicals and giving rise to many chemical
(sonochemical) reactions. At the same time,
streaming currents, extremely fast micro-jets (~ Fig 3.Phenomena of Acoustic Cavitation due to
Ultrasound
500 m/sec) and enormous shear forces are
generated in the cavitation filed, promoting a wide 3. Cellulose and its Composites-
range of physical (mechanical) effect
thus by sonication the biggest advantage that we 3.1 HISTORY
got over conventional synthesis method was
[3-5]Although several excellent reviews have been
reduction of time for synthesis and energy input as
published in the past few years on the application
well as all other steps like mechanical stirring were
of cellulose-based energy-related devices
ruled out which was highly advantageous and time
(including batteries, sensors, and other electronic
conserving.
systems), little attention has yet been paid to
cellulose-based supercapacitors When cellulose-
based supercapacitor applications have been
reviewed, the emphasis has mainly been on the use
of cellulose microfibers (CMFs) in
supercapacitors and less attention has been paid to
the use of nanocellulose fiber (NCF)- and
cellulose nanocrystal (CNC)-based devices. The
field of research associated with cellulose- based
sustainable supercapacitors is rapidly growing and
the rate of progress is currently very
high.Composites in supercapacitor applications
ELAN & NVISION 2018
are based on different cellulose building blocks
(i.e., CMFs, NCFs, and CNCs) and have
highlighted new trends in the field.
3.2 Structures and Properties
Cellulose is one of the most abundant,
natural, renewable and biodegradable polymers
[6].Cellulose can be found in wood, cotton, rice
straws, and sugarcane bagasse. Cotton Linters can
contain cellulose upto 90% which is maximum
among all other sources.The cellulose content in
all other sources varies as hemp(57%
cellulose),wood(40-50%) etc.(Fig.4)Cellulose is a
polysaccharide composed of D-glucopyranose
linked by 1,4-β glycoside bond. There are three
hydroxyl groups in cellulose; secondary -OH at
the C-2 and at the C-3, primary -OH at the C6
position. These hydroxyl groups in cellulose have
an important role in the compactness of the
crystalline structure and determines physical
properties of cellulose. At the plant fiber, cellulose
can be found in an amorphous phase which are
connected with crystalline phase through
intermolecular and intramolecular hydrogen
bonds. This is causing cellulose not to melt the
thermal degradation temperature .Cellulose has a
good mechanical properties, low density, and
biodegradable. There are several types of cellulose
(I, II, III, IV and V), cellulose I and II are
commonly found in nature. Cellulose I has a best
mechanical properties and a parallel chain
orientation, while cellulose II has anti-parallel
chain .Cellulose is a natural polymer which
insoluble in water because it has a long chain and
high molecular weight (more than 500.000 Da).
Cellulose in nanometers or nanocellulose has a
size range from 10 nm to 350 nm. Nanocellulose
has a higher surface area than cellulose, so nano-
cellulose can be one of the alternative solutions to
make cellulose more easily to modified and
dissolved in water.
Classification of Cellulose
Cellulose comes in basically 3 forms which are
classified on the basis of their size
ranges(Table.1).CMFs(CelluloseMicrofibres),CN
Cs(Cellulose Nanocrystals) and
NCFs(Nanocellulose fibres).Table 1 represents the
3
size based classification of cellulose with the order
of size ranges of various forms of cellulose
Table 1. Primary characterization
of various cellulose types
CMFs diameter Length
10m >10m
NCFs diameter: length:
10–80 nm <10m
CNCs diameter: Length~
5-30 nm 100nm
In the cell walls of plants, CMFs (with
thicknesses in the order of micrometers) are
embedded in a matrix consisting mainly of lignin
to form a composite which provides structural
support for the cell. Thinner NCFs (also
commonly referred to as microfibrillated cellulose)
can be extracted from CMFs using high-
pressure, high-temperature grinding or
microfluidization techniques.If acid
hydrolysis is used instead, CNCs (also
commonly referred to as nanowhiskers)
can be extracted. These cellulose
entities can be differentiated by their
thickness, the aspect (length to width)
ratios, and the molecular organization
of the fibers. This review discusses all
three cellulose fiber substrates: CMFs,
NCFs, and CNCs. Various methods can be
used to obtained nano-cellulose, such as acid
hydrolysis, ultrasonic technique, and enzymatic
hydrolysis [1,4,8.9]. The method that most widely
used is acid hydrolysis [7]. This method is easy
and fast to produce nanocellulose that has a better
properties. Some researchers have reported that
crystallinity index of nano-cellulose produced by
acid hydrolysis was higher than other methods.
The nano-cellulose obtained from the acid
hydrolysis also has a smaller size. These are the
reasons that acid hydrolysis method is selected to
obtained nano-cellulose. A Strong acid such as
H2SO4 and HCl is commonly used to break the
glycoside bonds in cellulose.There are several
steps involved in the obtaining of cellulose
nanofibres from cotton linters using acid
hydrolysis method and sonochemical technique
which are discussed below. Nanocellulose is used
in the various field such as a barrier in the
separation process of hazardous waste, food
wrappers which replace the non-biodegradable
plastics, and as nanocomposite to improve
properties such as mechanical, thermal, ionic
conductivity properties of the polymer.
Polyaniline and its properties
ECPs, such as polypyrrole (PPy), polyaniline
(PANI) and polythiophene, are particularly
interesting as electrode materials because of their
inherent fast redox switching, high conductivity,
low weight, and straightforward manufacturing
processes, in addition to the possibility of
extracting the monomers from biomass material
Besides, PANI is inexpensive with good
environmental stability, redox reversibility, and
electrical conductivity . The PANI-based
supercapacitors could offer a high-performance
and low-cost alternative source of energy to
replace rechargeable batteries for various
applications, such as electrical vehicles and high
power tool. There are various methods used to
synthesize PANI, such as emulsions , template
synthesis , self-assembly , and interfacial
polymerization . However, large amounts of
surfactants are usually needed, which could make
PANI difficult to attach the substrate without
involving large contact resistance . The
electrochemical synthesis of PANI is simple and
low-cost. The adherent films of PANI on the
substrate can be easily prepared by the
electrochemical deposition and can be directly
used for electrochemical studies
PROCEDURES
A. Nanocellulose Fibres from Cotton linters
The linter were collected from a cotton trader or
specifically from any cotton productions(Fig.5).It
was subjected to acid hydrolysis using
concentrated H2SO4 acid(98%v/v). A Strong
acid such as H2SO4 and HCl is commonly used to
break the glycoside bonds in cellulose through
Hydrolysis process . There are several steps in
acid hydrolysis: (1) strong acid hydrolysis of
cellulose under controlled conditions such as acid
concentration, time, temperature, and ratio of the
acid to cellulose.We have considered a ratio of
1:2(w/v) with concentrated sulphuric acid at room
temperature. (2) dilution with some water to stop
hydrolysis process and repeated washing with
successive centrifugation; (3) In place of
mechanical stirring, sonication using probe
sonicator cut down the time of upto 4hrs stirring
to 20 min sonication .Sonication also helped in
forming a stable suspension of nano-cellulose
which was later subjected to centrifugation at
around 13,000rpm for an interval of 15 minutes.
(5) drying of the suspension to yield solid nano-
cellulose.
B. Synthesis of Polyaniline from aniline
In one beaker make the 50 ml solution of 1.0M
HCl and add 0.2M aniline into it. In another
beaker make 0.25M solution of ammonium
persulphate in 1.0M HCl. Keep both solutions for
1 h at room temperature (~18–24 °C), then mixed
in a beaker,put under bath sonicator, and left at
rest to polymerize. Next day, the PANI precipitate
was collected on a filter, washed with three 100
ml portions of
0.2 M HCl, and similarly with acetone. Polyaniline
powder was dried in vacuum at 80 °C for
overnight. Next day crushed and taken for further
use[10].
The above synthesised composites of
polyaniline and cellulose nanofibres can be used
for preparing the electrodes of
supercapacitors.Polyaniline nanoparticles were
the surface of cellulose composites.
Fig4.Cellulose molecule structure
ELAN & NVISION 2018 5

The contens of the paper were extracted from

various research papers and books,journals
published on synthesis of electrode materials for
supercapacitors whose references have been
mentioned below.

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CONCLUSION Ajayan, Proc. Nat.
In the above work,the need for the development
of supercapacitors as the energy source was
discussed along with the working principle
underlying it.The cellulose based supercapacitors
with the coating of electrically conductive material
i.e. Polyaniline, over it have proved themselves as
one the most favourable energy sources in past
few years.The in-situ facile synthesis of cellulose
nanofibres was discussed along with the synthesis
of polyaniline from its monomer aniline.The
presented work enforced on the possibilities and
needs of The cellulose based supercapacitors with
the coating of electrically conductive material i.e.
Polyaniline, over it have proved themselves as one
the most favourable energy sources in past few
years

ACKNOWLEDGEMENT