Development of Ternary Nanocomposite of Reduced Graphene Oxide,

Polyaniline, High Entropy Alloy for Supercapacitor Applications

A Project report submitted

in partial fulfilment of the requirements for the award of the degree of

Bachelor of Technology
in
Metallurgical and Materials Engineering

by
Jatin Gopal (2019BMME032)
Manisha Meena (2019BMME014)
Sahil Chahal (2019BMME043)
Harish Sankhi (2019BMME055)

Under the Supervision of

Dr. Irfan Samad Wani
Assistant Professor

Department of Metallurgical & Materials Engineering

National Institute of Technology Srinagar
Hazratbal, Srinagar (190006), J&K, India

June, 2023
 DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING
NATIONAL INSTITUTE OF TECHNOLOGY SRINAGAR

CERTIFICATE

This is to certify that the project entitled “Development of Ternary Nanocomposite of Reduced
Graphene Oxide, Polyaniline, High Entropy Alloy for Supercapacitor Applications”
Submitted by Jatin Gopal (2019BMME032), Sahil Chahal (2019BMME043), Manisha Meena
(2019BMME014) & Harish Sankhi (2019BMME055) to the National Institute of Technology
Srinagar for the award of the degree of Bachelor of Technology in Metallurgical and Materials
Engineering is a bonafide record of project work carried out by them under my supervision and it
has not been submitted elsewhere for the award of any degree or diploma.

Dr. Irfan Samad Wani

Assistant Professor
Department of Metallurgical and Materials Engineering
National Institute of Technology Srinagar Hazratbal,
Srinagar (190006), J&K, India
Place: NIT Srinagar
Date: June 19th,2023

Project Viva - Voce examination held on June 19th 2023

Supervisor Project Coordinator Member External Examiner HOD

 CANDIDATE DECLARATION

We hereby declare that the project report entitled “Development of Ternary Nanocomposite of
Reduced Graphene Oxide, Polyaniline, High Entropy Alloy for Supercapacitor
Applications” is submitted in partial fulfillment of the requirements for the award of the degree
of Bachelor of Technology in Metallurgical and Materials Engineering represents our own ideas
and where other ideas or words have been included, we have adequately cited and referenced the
original sources. This report is an authentic record of bonafide work carried out by us during 7 th
and 8th semester under the supervision of Dr. Irfan Samad Wani. We also affirm that the results
presented in this report have not been submitted by us anywhere for the award of any degree or
diploma.

Jatin Gopal Manisha Meena

2019BMME032 2019BMME014

Sahil Chahal Harish Sankhi

2019BMME043 2019BMME055
 ACKNOWLEDGEMENT

We would like to express our gratitude and special thanks to our project supervisor Dr. Irfan Samad
Wani for his time, guidance, and support. We thank him for allowing us to undertake this project
and providing us all the resources required for the project. We are highly thankful to our supervisor,
who gave us the wonderful opportunity to work on and explore the field of Nanotechnology. It
was a kind of new experience for us that gave an insight into the modern trends in Material Science.
We express our gratitude to Er. Hameem Habib (Research Scholar) & Er. Tahir Ahmad Dar
(Research Scholar) who were always there to help us. Their experience was key to this project.
We would like to express our gratitude to Prof. Atikur Rahman, HOD Metallurgical & Materials
Engineering and other faculty members. Also, thankful to all the laboratory staff and library staff
for helping us to complete this work with their immense support.
Lastly, we are grateful to the members present at Central Research Facility, NIT Srinagar for their
much-needed help in giving us access to the hi-tech analysis machines.

Jatin Gopal Manisha Meena

2019BMME032 2019BMME014

Sahil Chahal Harish Sankhi

2019BMME043 2019BMME055

I
 Abstract

The increasing demand for the development of high-performance supercapacitors led researchers
to synthesize and develop new electrode materials by optimizing various parameters. In this
respect, we have developed ternary nanocomposites using reduced graphene oxide, polyaniline
and high entropy alloy as potent electrode material. We have used simple sonication-assisted
mechanical mixing of synthesized reduced graphene oxide, polyaniline and high entropy alloy at
varied proportions. The prepared composite have been analyzed by different characterization
techniques such as XRD, SEM-EDS and Raman Spectroscopy to comprehend the successful
formation of the rGO, polyaniline, HEA and composite. The electrochemical characterizations
revealed that the nanocomposite shows the specific capacitance of 961.8 F g−1 at a different
voltages 10mvs, 50 mvs, 100 mvs with excellent capacity retention of 92% even after 3 GCD
cycles. The method is promising to fabricate electrode materials for high performing
supercapacitors combining reduced graphene oxide, polyaniline and high entropy alloy.

II
 Table of Contents

Acknowledgement I
Abstract II
Table of Contents III
List of Figures IV

1. Introduction 1
2. Literature Review 5
3. Objectives of Project work 11
4. Experimental Planning 12
5. Experimental Procedure 13
6. Results and Discussion 18
7. Conclusion 27
8. References 28

III
 List of Figures

Fig. no. Figure PAGE

No.
1 Comparative graph between Capacitor, Supercapacitor 02
and battery showing difference in energy density and
power density
Schematic representation of different type of 03
2 supercapacitor.
A 2D hexagonal lattice of carbon atoms make up
3 04
graphene.
4 Schematic ternary and quaternary alloy systems, showing 06
regions of the phase diagram that are relatively well known
(green) near the corners and relatively less well known
(white) near the center.
The areas of physical metallurgy influenced by four core effects
5 07
of HEAs
(a) Schematic presentation of the graphene’s hexagonal
6 08
lattice structure. (b) Three most typical graphite structures
and stacking arrangements of graphene and (c) Schematic
of the outplane π orbitals and in-plane σ bonds
perpendicular to the plane of the graphene sheets.
7 Schematic representation of different methods of graphene 10
synthesis.
‘Scotch tape’ graphene synthesis procedure, first reported
8 11
in 2004 by Novosel Ov and Giem.
A schematic diagram showing the growth mechanism for
9 12
CVD Graphene growth on Ni substrate. (a) Graphene
growth by dissolution-precipitation mechanism and (b)
Graphene growth direct by deposition mechanism.

10 Synthesis of Graphene Oxide by Modified Hummer’s 13

Method

11 Schematic of Electrochemical measurement 14

IV
12 Synthesis of Graphene by Modified Hummer’s Method 20
(a) Magnetic Stirrer with ice bath, (b) Greenish black
solution and (c) Deposition of GO settle at the bottom of
the beaker.
Synthesis of reduced graphene oxide (a) sonication of
solution for 2h, (b) solution kept at hot plate for 12h for
13 20
drying and (c) synthesised reduced graphene oxide.

14 Synthesis of Polyaniline (PANI) (a) showing soln. of APS 21

and distilled water slowly added to aniline soln. using
burette and (b) synthesised Polyaniline (PANI).
Synthesis of HEA (a) Hi-Speed Planetary Ball Mill and (b)
15 22
synthesised HEA (AlCoCrFeNi).
(a) Showing soln. of APS and distilled water slowly added
16 23
to soln. using burette (b) synthesised nanocomposite
retained over Filter paper.
17 (a) sonication of solutions for 2h (b) Electrode (c) 24
Electrochemical Spectroscopy Setup.
18 XRD of GO, rGO, PANI, HEA at 0hr, HEA at 10hr, HEA 27
at 20hr, HEA at 30hr and rGO+PANI+HEA
nanocomposite
19 29
(a) The SEM-EDS elemental mapping of the fabricated
AlCoCrFeNi HEA by mechanical alloying (b) The SEM-
EDS elemental mapping of rGO + PANI + HEA
composite
20 Raman spectra of rGO. 30

(a) Depicts the CV curve of the different 32

21 electrodes(PANI/Hea/rGO/Composite)

22 (a) rGO GCD graph (b) Composite GCD graph (c) HEA 34
GCD graph (d) PANI GCD graph

V
 CHAPTER: 1

INTRODUCTION

The exhaustion of fossil fuel and continuous accumulation of greenhouse gasses urge the
community to investigate new and highly sustainable energy storage technology . In the 21st
century, low cost and environmentally benign energy storage devices that have high energy and
power density, and are compatible with solar, wind, and nuclear energy-harvester setup, such as
batteries and supercapacitors, are studied to address the problems of climate change, as well as to
suffice the urgent need for efficient energy storage . Energy storage devices are widely used in the
fields of portable electronic devices (such as smart phones, laptops, cameras, and watches),
transportation (e.g., electric vehicles), medical area, and defense. For instance, batteries are
employed due to their high energy density and capability to store a large amount of energy.
However, the low power densities of batteries caused by their non-ideal conductivity, volume
variability, and other barriers limit their potential use in many areas. As an effective and well-
studied alternative, supercapacitors are being extensively investigated as promising energy storage
devices.

Developed in 1970s, supercapacitors are promising electrochemical devices that can store energy
by polarizing the electrolyte. Supercapacitors are a kind of energy storage devices with
performance sitting in between batteries and traditional capacitors as shown in fig. 1. They have
attracted considerable attention due to their high power density, short charging time, long lifespan,
and excellent safety. Supercapacitors can be charged and discharged at high rates, can be operated
at low and high temperatures, and has minimal fading rate compared with batteries. Supercapacitor
devices have been developed and applied for commercial use in the past 25 years. However,
producing supercapacitor devices with high power density without sacrificing their energy density,
long span life, fast charge/discharge, and environment-friendly features remain a big challenge.
Likewise, the practical applications of supercapacitors have been severely hindered given their
low energy density, complex fabrication, and high cost. Thus, optimization of the electrode

1
materials of supercapacitors is one important key strategy for improving the performance of
supercapacitor devices.

Various electrode materials of supercapacitors have been extensively investigated. Among them,
typical oxide/sulfide/nitride/phosphide/boride/ferrite- and polymer-based electrode materials can
deliver high energy density, but they have poor cycle life and relatively low power density. By
contrast, carbon-based electrode materials exhibit excellent life cycle and fast
charging/discharging, but their low energy density limits their practical applications.

In the past years, supercapacitors were only classified according to the nature of material: carbon-
based and metal-based materials. These materials are well-categorized accordingly into their
storage mechanism: electric double layer capacitive (EDLC) and pseudocapacitive, respectively.
EDLCs store energy via the adsorption of the electrostatic charges on the surfaces of the
electrode/electrolyte, whereas the pseudocapacitance is based on the fast surface redox reaction.
In 1999, Brian Evans Conway conducted fundamental experiments on ruthenium oxide
electrochemical capacitors to explain the increased capacitance caused by surface redox reactions
with Faradaic charge transfer between electrodes and ions.

Fig. 1. Comparative graph between Capacitor, Supercapacitor and battery showing difference in energy density and
power density

2
In the past years, supercapacitors were only classified according to the nature of material: carbon-
based and metal-based materials. These materials are well-categorized accordingly into their
storage mechanism: electric double layer capacitive (EDLC) and pseudocapacitive, respectively.
EDLCs store energy via the adsorption of the electrostatic charges on the surfaces of the
electrode/electrolyte, whereas the pseudocapacitance is based on the fast surface redox reaction as
shown in fig. 2. In 1999, Brian Evans Conway conducted fundamental experiments on ruthenium
oxide electrochemical capacitors to explain the increased capacitance caused by surface redox
reactions with Faradaic charge transfer between electrodes and ions.

With these initial classification systems, the storage mechanism is greatly depending on the nature
of the material used, provided they are using the sole source of precursor either as carbon- or metal-
based materials. Through the years, material developments have evaluated mono-metallic to
trimetallic oxides, and/or carbon to carbon-metal based combinations. Having multi-component
electrode materials consisting of combined carbon-based and redox active-based materials behave
differently depending on which controls the overall storage mechanism. As more researchers are
studying the mechanism in depth, quantitative measurements in defining the mechanism of energy
storage are introduced and successfully conveyed, such as quantitative calculations done by
Trasatti and Dunn that benefits electrode materials that has more than one component (e.g. hybrid
electrodes). Thus, it is important to classify supercapacitors, accordingly, given the growing
numbers of combinations in developing multi-material electrodes for supercapacitors.[11]

Fig. 2. Schematic representation of different type of supercapacitor

3
Graphene : To understand the graphene history, some terms such as carbon, graphite, and
graphene are important to be discussed. Carbon, the most abundantly element on earth, takes its
name from the Latin word carbo meaning charcoal. Carbon forms many allotropes with many
potential applications. The major ones known since antiquity are graphite and diamond. Until the
mid-1980, carbon was believed to exist in two only physical forms which are diamond and
graphite, and it were in 1985 that fullerene cluster, a new form of allotropes of carbon was
discovered. It was believed that graphite was a lead ore and was called “plumbago”. In 1779,
Scheele demonstrated that plumbago is actually carbon, not lead since people used it to write marks
on their sheep, Verner (1789) named it graphite (a Greek word for “writing”). During the Middle
Ages, the weak dispersion forces in between the adjacent sheets and layers were utilized to produce
marking instruments, just in the similar way that we make pencils today from graphite.[1,3,5]

Unbeholden and Lewis (1960) isolated a mono-atom plane of graphite and pointed out that
graphite consists of layers, which are a network of hexagonal rings of carbon atoms. Therefore,
the single carbon atomic layer of graphite may compactly arrange into a two-dimensional (2D)
honeycomb lattice known as graphene.[5]

However, it is in 2004, when Novosel Ov and Giem successfully isolated and studied a single-
atom-thick crystallite (graphene) from bulk graphite and transfer them onto thin silicon dioxide on
a silicon wafer by a famous Scotch Tape Technique that the properties of graphene material were
achieved. It is noted that, the first graphene was extracted from graphite using a technique called
micromechanical cleavage and the Nobel Prize in 2010 was awarded jointly to Konstantin Novosel
Ov and Andre Giem in Physics “for groundbreaking experiments on the two-dimensional material
graphene”. Currently, graphene is a trending nanomaterial which is replacing silicon in different
applications across various research fields.[2,3]

Fig. 3. A 2D hexagonal lattice of carbon atoms make up graphene

4
High Entropy Alloys (HEAs) are defined as alloys with five or more principal elements having
equal atom percentage. Each principal element should have a concentration between 5 and 35
atomic %. Existence of HEAS were firstly reported by Scientists Yeh J.W & Huang K.H in 1996.

Although HEAS were described as early as 1981 and 1996, significant research interest did not
develop until after independent 2004 papers by Jien-wei Yeh and Brain Cantor, with Yeh's first
paper on the topic published 2 months sooner. Yeh also coined the term "high- entropy alloy" when
he attributed the high configurational entropy as the mechanism stabilizing the solid solution
phase. Cantor, not knowing of Yeh's work, did not describe his alloy as a "high-entropy" alloy, but
the base alloy he developed, Equiatomic FeCrMnNiCo, has been the subject of considerable work
in the field.[14]

High entropy alloys (HEAs), contain five or more component metal atoms in a single-phase solid
solution structure. The preference to form solid solution over intermetallic compounds between
component metal atoms is essentially due to the high configurational entropy of the solid solution
phase1–3. Several reports have illustrated the relevance of factors such as high configurational
entropy, lattice distortion, sluggish diffusion and cocktail effect in high entropy alloys1–6. HEAs
exhibit several useful properties such as high corrosion resistance, high wear resistance, high
strength and excellent oxidation resistance 7–12.[14]

HEAs are loosely defined as solid solution alloys that contain more than five principal elements in
equal or near equal atomic percent (at. %). The multi-component Equimolar alloys should be
located at the center of a multi-component phase diagram, and their configuration entropy of
mixing reaches its maximum for a solution phase the information and understanding are highly
developed on alloys close to the corners and edges of a multi-component phase diagram, with
much less knowledge about alloys located at the center of the phase diagram, as shown
schematically for ternary and quaternary alloy systems (fig. 4). This imbalance is significant for
ternary alloys but becomes rapidly much more pronounced as the number of components increases.
For most quaternary and other higher-order systems, information about alloys at the center of the
phase diagram is virtually nonexistent except those HEA systems that have been reported very
recently

5
 .

Fig. 4. Schematic ternary and quaternary alloy systems, showing regions of the phase diagram that are relatively
well known (green) near the corners and relatively less well known (white) near the center [13]

Four core effects: High-entropy effect, Sluggish diffusion effect, Severe lattice-distortion effect,
Cocktail effect [13,14]

1. High-entropy effect: This tend to stabilize the high-entropy phases, e.g., solid-solution phases.
The effects were very counterintuitive because it was expected that intermetallic compound phases
may form for those Equi- or near Equi-atomic alloy compositions which are located at the center
of the phase diagrams The high-entropy effect is mainly used to explain the multi-principal-
element solid solution. According to the maximum entropy production principle (MEPP), high
entropy tends to stabilize the high-entropy phases, i.e., solid-solution phases, rather than
intermetallic phases.[13,14]

2. Sluggish diffusion effect: The sluggish diffusion effect is usually used to explain the formation
of nano-sized precipitations, because the nuclei are easier to form but grow slowly. [1,2] HEAs
are usually very complicated, which can include nano-precipitates, ordered solid solution phases,
disordered solid-solution phases, and even amorphous phases. [13]

3. Severe lattice-distortion effect: This effect is usually compared with the one dominant element
alloys, where the lattice site is occupied mainly by the dominant constituent. For HEAs, each
element has the same possibility to occupy the lattice site, if ignoring chemical ordering. Since the
size of different elements can be very different in some cases, this can lead to the severe lattice
distortion. This effect is well confirmed by the ultrahigh strength of the BCC HEAs. The severe

6
lattice distortion is also used to explain the high strength of HEAs, especially the BCC-structured
HEAs. The severe lattice-distortion effect is also related to the tensile brittleness and the slower
kinetics of HEAs.[13]

4. Cocktail effect: For metallic alloys, the effect indicates that the unexpected properties can be
obtained after mixing many elements, which could not be obtained from any one independent
element. The cocktail effect for metallic alloys was first mentioned by Ranganathan, which has
been subsequently confirmed in the mechanical and physical properties. The cocktail effect implies
that the alloy properties can be greatly adjusted by the composition change and alloying.[13]

Fig. 5. The areas of physical metallurgy influenced by four core effects of HEAs.[17]

7
 CHAPTER: 2

LITERATURE SURVEY

2.1 Crystal Structure and Characteristics of Graphene

A single atom thick planar sheet of sp2-bonded carbon atoms packed closely together in a
honeycomb lattice crystal makes up the two-dimensional layers that make up the carbon
nanomaterial known as graphene. Figure 6a shows the structure of graphene, which is analogous
to several joined benzene rings with hydrogen atoms swapped for carbon atoms. Due to the lack
of oxygen groups, graphene is thought to be hydrophobic. Additionally, it has a plane of sp2
connected atoms with a molecule bond length of 0.142 nm, making it a carbon allotrope. Graphite
is made up of layers of graphene with an inter-planar spacing of 0.335 nm.[3]

Fig. 6. (a) Schematic presentation of the graphene’s hexagonal lattice structure. (b) Three most typical graphite
structures and stacking arrangements of graphene and (c) Schematic of the out-plane π orbitals and in-plane σ bonds
perpendicular to the plane of the graphene sheets.[4]

Besides, graphene is naturally a semimetal and its benzene ring-like electronic structure comprises
of six π-orbitals with three occupied bonding and three unoccupied antibonding orbitals, separated
by a bandgap. Fusing of these benzene rings leads to a little overlap between the valence and

8
conduction bands thus the electrons from the top valence band can flow to the bottom conduction
band without stimulating any heat (Fig. 6). Aggregation of the layers of graphene determines the
specific surface area. The modification of pristine graphene with other compounds decreases the
aggregation and increases the effective surface area. In recent years, graphene has fascinated much
attention of researchers, owing to its extraordinary electronic, optical, magnetic, thermal, and
mechanical properties as well as large surface area[1].

2.2 Synthesis Techniques of Graphene

Recently, a number of techniques have been employed to synthesize graphene. Depending on the
purity and the final product desired, this manufacturing process is referred to as extracting
graphene. Different methods were discovered to create layers and thin films of graphene following
its discovery in 2004. Some of the popular techniques for producing graphene include chemical
vapor deposition (CVD), chemical exfoliation, chemical synthesis, and mechanical cleaving[6].

Top-down and bottom-up synthesis methods are determined by the number of layers, thickness,
the nature and average size of the graphene materials. In top-down growth mechanism process,
graphene sheets are produced by exfoliation/separation of graphite and its derivatives including
graphite oxide (GO). Figure 7 summarizes both top-down and bottom-up synthesis methods.[2]

9
 Fig. 7. Schematic representation of different methods of graphene synthesis[5]

➢ Mechanical Exfoliation

It was the first method to be used by Novosel Ov and Giem for the production of graphene with
the help of an adhesive tape to force the graphene layers apart. This technique leaves numerous
layers of graphene on the tape after it has been peeled off, but subsequent peeling causes it to
split open into a few graphene flakes. For detachment, the tape is bonded to a specific substrate
(acetone), and a final peeling with new tape is performed to create flakes that are distinct in size
and thickness and can be seen on SiO2/Si surfaces with a light microscope. Due to the slow and
erratic nature of this process, graphene is most frequently studied rather than exploited for practical
purposes in industry. This procedure can also be carried out by employing other agents, including
an electric field, epoxy resin, and transfer printing.[1,2]

10
Fig. 8. ‘Scotch tape’ graphene synthesis procedure, first reported in 2004 by Novosel Ov and Giem. Adapted from
Ref. Copyright 2012 Nature.

➢ Chemical Exfoliation

Graphite exfoliation by electrochemical techniques has become a simple but yet high yielding
method in recent times for the mass pro- duction of graphene. This method involves the use of
various forms of graphite such as graphite foils, plates, rods and graphite powders as electrodes in
an aqueous or non-aqueous electrolyte and electric current to bring about the expansion of
electrodes. The electrodes could be of two types based on the power applied, that is, Cathodic
(Negative) and Anodic (Positive) electrodes. Wang et al. in their study used Pure Graphite as
electrodes and PSS (Polysodium-4-styrenesulfonate) solubilized in deionized water to incarnate
the electrolyte. They accommodated the graphite rods in an electrochemical cell which was filled
with the electrolyte. A persistent current of 5 V was applied. Few minutes of electrolysis resulted
in the accumulation of a black material at the anode. The exfoliation process was carried on for 4
h to isolate the product from the cell. It was then centrifuged at 1000 rpm and then the product was
gradually poured out. The dispersion obtained was found to be extremely stable. Powdered dry
graphene was achieved by washing the dispersion with deionized water and alcohol followed by
vacuum drying. Then the yield was calculated by weighing the dry powder and sediment.[10]

➢ Chemical vapor deposition

11
Chemical vapor deposition (CVD) is a bottom-up synthesis technique used for production of
high quality graphene on a large-scale basis. CVD is one of the most widely used technologies
for producing high-quality graphene.[10]

This method involves combining a gas molecule with a surface substrate inside a reaction chamber
under temperature, pressure, and gas flow rate conditions. A typical CVD instrument includes a
quartz reaction chamber, a mass flow controller, a pump, thermocouples for temperature
measurement, a gas delivery system, a vacuum system, an energy system and a computer for auto
control. Different substrates are used in CVD for graphene film growth, they include Nickel (Ni),
Copper (Cu), Iron (Fe), and Stainless steel. Methane (CH4) and acetylene (C2H2) are normally
used as a carbon source.[2]

CH4(g) —— greater than 2H2 (g) + C(S) (ii) C2H2(g)— –> H2(g) + 2C(s)

Hydrogen and argon gas are used as carrier gases to remove and clean unwanted oxides on the
metal catalyst surface. This growth process follows two main steps:

i. Formation of carbon by pyrolysis of the gas precursor.

ii. The formation of the carbon structure of graphene using the segregated carbon on the
surface of the metal catalyst.

12
Fig. 9. A schematic diagram showing the growth mechanism for CVD Graphene growth on Ni substrate. (a) Graphene
growth by dissolution-precipitation mechanism and (b) Graphene growth direct by deposition mechanism.[5]

➢ Modified Hummer’s Technique

Marcano et al. modified the Hummers method. A modified Hummer's technique was used to
produce graphene oxide (GO) from graphite powder. In short, 1 gramme of graphite and 0.5
gramme of sodium nitrate were mixed, then 23 ml of concentrated sulphuric acid was added while
constantly stirring. After one hour, 3 grammes of KMnO4 were gradually added to the above
solution while keeping the temperature below 20°C to avoid overheating and explosion. The
mixture was agitated for 12 hours at 35 °C, and the resultant solution was diluted by adding 500
ml of water while vigorously stirring. To guarantee that the reaction with KMnO4 was completed,
the suspension was treated with a 30% H2O2 solution (5 ml). The resultant mixture was washed
with HCl and H2O, followed by filtering and drying, yielding graphene oxide sheets.[3]

Fig. 10. Synthesis of Graphene Oxide by Modified Hummer’s Method.[5]

2.3 Electrochemical measurements

Cyclic voltammetry (CV) :The CV analysis of electrodes was carried out to examine
the potential of each synthesized material in electrical charge storage. Specific
capacity was calculated using the following formulae:

13
 C = ∫ iVdV/μmΔV*2 .eq.(1)

where, ∫iVdV is generally the area below the CV curve diagram, V and i are
potentials and currents in CV analysis. ΔV is the potential window, m is the mass of
active substance used, and μ is the potential scan rate .

Galvanostatic charge discharge (GCD) : Galvanostatic charging-discharging

(GCD) is the utmost precise technique for capacity measurements. The GCD
techniques have contrived the specific capacity and sustainability of all the samples
of HEA/PANI/RGO/COMPOSITE electrodes

The specific capacitance (Cdsp), energy density (E), and power density (P)
measurements from GCD plots were carried out using the following equations,

C= I*T/ΔV*m *2

Fig. 11. Schematic of Electrochemical measurement.

Mechanism of Oxidation of Polyaniline : We propose the following mechanism for autogeneous

oxidation of polyaniline

−NH− + H+ →−N+H2−−NH−+H+→−N+H2− (1)

−N+H2−↔−N·+H−+ H·−N+H2−↔−N·+H−+ H (2)

14
The first step involves the protonation of the amine nitrogen of polyaniline. This step is followed
by the generation of a polaron and a hydrogen radical, H·H·. Oxygen reacts with H·H· to form
water.

4H·+O2 → 2H2O4H·+ O2→ 2H2O (3)

Hence oxygen merely hastens the autogeneous oxidation process.

There is also a possibility of a parallel mode where oxygen can directly oxidize the reduced form
of polyaniline to produce polarons as suggested by Khomenko et al. [4].

4−NH+2−+O2→4−N·+H−+2H2O+4e−4− NH2+ − + O2 → 4−N· + H− + 2H2O + 4e− (4)

Electrons released through this reaction may react with hydrogen ions to produce H+ radicals.

Mechanism of Reduction : We propose the following mechanism for the reduction reaction of:
polyaniline film. It consists of the following step:

−N·+H− + H2O → HO.+ −N+H2− (5)

Reaction 5 produces a hydroxyl radical [Link]., thereby reducing the polaron to protonated
amine. The reduction of polarons in the film causes a reduction in its potential as the protonated
amine groups do not contribute to the capacitance of the film.

2.4 SUMMARY OF LITERATURE SURVEY

Anu Saini et al. [2016] reported graphene Oxide (GO) was prepared from graphite powder using
modified Hummer’s method, followed by reduction of exfoliated GO with hydrazine hydrate
which resulted in formation of high surface area 2D structure consisting of RGO flakes and
nanosheets. To obtain porous and layered structure of RGO, hydrothermal reduction was
performed at an elevated temperature. In XRD results, it was found that 2Θ = 26.4° peak with
interplanar spacing (d002) of 0.35nm of graphite powder disappeared, while another significant
peak observed at 2Θ =11.95° with interplanar spacing of 0.754 nm demonstrated successful
oxidation of graphite and formation of GO. SEM results also support the formation of RGO since
particle size lies in nanometric range (6-20 nm).[4]

15
Vestince B. et al. [2021] reported graphene's characterization involves investigation of its
morphology, properties, defects, and layers based on spectroscopic and microscopic
measurements. By Raman Spectroscopy, three main peaks are observed in graphene and include;
D (1350 cm− 1), G(1580 cm-1) and 2D(2700 cm−1) peaks. By XRD, the graphite peak occurs at
26.6 degrees.[2]

S. Srinivasan et al. [2021] reported that next 20-30 years the key component of electronics
industry will be graphene. It has come out exhibiting very unique and fascinating properties in all
domains. We discuss aspects of how graphene could be used in mainstream electronic devices.
Main focus is on signal processing in high-volume, industrially-manufactured battery-powered
devices e.g. mobile phones and laptops. We find that there is a characteristic length scale l0,
defined as Dh0 / 4G, where D is the stiffness of the graphene sheet, h0 and G are the height of
interlayer crosslink and shear modulus respectively. The DTS is then applied to predict the
mechanics of graphene-based paper materials under tensile loading.[1]

Hamid et al. [2016] reported nickel sulfide wrapped with graphene and utilized in Li-ion batteries
and supercapacitors. Significant improvement of nickel sulfide was observed by graphene
wrapping not only in the performance of Li-ion battery but also in the performance of
supercapacitor electrode. The specific capacity of nickel sulfide wrapped with graphene as anode
for Li-ion battery was observed above 1200 mAh/g cycles with improved rate capability. The
specific capacity of nickel sulfide wrapped with graphene as supercapacitor electrode was
observed around 1000 F/g and current density of 55A/g.[7]

Wei Liu et al. [2018] reported metal sulfides with graphene composite for supercapacitors. The
resultant composite also bears excellent mechanical integration and conductivity. It gives a high
capacitance value of 310.2 C g−1 and shows an outstanding rate capability of 61.8% retention.
The fabricated graphene composites depict high cycling stability over 10000 cycles.[8]

Pattarachai Srimuk et al. [2015] reported a composite of rGO/copper oxide. The composite of
rGO - copper oxide was fabricated by an ultra-sonication mixing of copper oxide and rGO. A

16
simple spray coating technique was used to fabricate the supercapacitor electrode material of 10
wt% rGO composite exhibits a capacitance value of 385 F/g at 1A/g. [9]

Kong et al. [2019] reported AlCoCrFeNi HEA as electrodes for supercapacitors. The nanoporous
binder-free HEAs was synthesized by selective phase dissolution in H2SO4. The HEAs exhibited
a high volumetric capacitance of ~700 F cm− 3 and retained 97% after 3000 cycles. [14]

Jin et al. [2018] reported high entropy metal nitride (HEMN) cubic structure composed of
VCrNbMoZr through urea method assisted by mechanochemical synthesis. The HEMN exhibited
54 F g–1 at a very high scan rate of 200 mV.[16]

17
 CHAPTER: 3

OBJECTIVE OF PROJECT WORK

From the Literature survey it is concluded that by combining HEA and graphene nanoparticle there
is possibility to further optimize the electrochemical behavior of HEA materials.

➢ Chemical Synthesis of Reduced Graphene Oxide via modified Hummer’s Method.

➢ Chemical Synthesis of Polyaniline (PANI).

➢ Synthesis of High Entropy Alloy (AlCoCrFeNi) by Ball Milling.

➢ Formation of Nanocomposite of HEA, PANI and rGO.

➢ Characterization analysis Via X-Ray Diffraction Method, Scanning Electron Microscopy,

Raman Spectroscopy and Electrochemical Spectroscopy.

18
 CHAPTER: 4

EXPERIMENTAL PLANNING

19
 CHAPTER: 5

EXPERIMENTAL PROCEDURE

5.1 Synthesis of Reduced Graphene Oxide by Modified Hummers Method

Raw Materials Required Graphite Flakes (Sigma Aldrich, 99.99 Purity), NaNO3 (CDH), H2SO4
solution, KMnO4 (30 grams), Distilled Water, H202 Aqueous Solution.

5.1.1 Preparation of Graphene Oxide : 5 g of Graphite Flakes and 5 g NaNO3 were added into
a beaker and further 230ml of H2SO4 was used to mix the powder. The solution was stirred for 4
hrs. at 200 rpm by placing the beaker in an ice bath to control the temperature as shown in Fig.
12(a). After 4 hours of stirring, 30 gm of Potassium Permanganate KMnO4 was added slowly into
the solution and stirred for 1 hr. by maintaining the temperature using ice bath. The ice bath was
removed, and the solution mixture was stirred at 35 °C for 1 hr, the colour of the solution changes
from dark black to greenish colour as shown in figure 12(b). The mixture was diluted with 450 ml
of distilled water at 35 °C, care should be taken to add the DI water slowly to avoid the increase
in temperature. After addition of DI water, the temperature was increased to 90 °C and stirred for
2 hours. After completion of this step the solution was cooled to room temperature. Further 1 ltr.
of DI water and 100 ml H2O2 was added in the solution and stirred for 1 hour at room temperature.
The colour of the solution at this stage change into light yellow. The aqueous suspension is kept
undistributed for overnight so that the deposition of graphite oxide will settle at the bottom of the
beaker as shown in figure 12(c). The solution was decanted from the beaker and 5% HCl was used
to wash the graphite oxide sedimented at the bottom of the beaker, subsequently it was washed
with deionized water for several times until its pH reaches 7. Lastly, the collected viscous GO was
heated in the oven at 600C to obtain the GO powder.

20
Fig. 12. Synthesis of Graphene Oxide by Modified Hummer’s Method (a) Magnetic Stirrer with ice bath, (b) Greenish
black solution and (c) Deposition of GO settle at the bottom of the beaker. [MME Department, NIT Srinagar]

5.1.2 Synthesis of Reduced Graphene Oxide

To synthesis the Reduced Graphene Oxide through chemical method following procedure was
followed:

Take 0.5 grams of Graphene Oxide in 300 ml of distilled water and sonicate the solution for
2 hours. The beaker was kept on the hot plate at 40° C & stirred for 15 minutes. 800 μl
(microliters) of Hydrazine Hydrate (H.H) were added drop by drop with the help of
micropipette. After addition of HH, the temperature of the hot plate was raised to 80 C and
stirred for 24 hours. Then the solution was kept for drying on the heating plate for 12 hour.
After 12 hour dried rGO was collected as shown in figure 13(c).

(a) (b) (c)

21
Fig. 13. Synthesis of reduced graphene oxide (a) sonication of solution for 2h (b) solution kept at hot plate for
12h for drying and (c) synthesised reduced graphene oxide. [MME Department, NIT Srinagar]

5.3 Synthesis of Polyaniline (PANI)

To synthesis the PANI, ice bath was used to control the temperature and initially 50 ml of
Distilled water was used and in this 4.10 ml of HCL was added. Separately 1 ml of Aniline
was kept in the beaker in which the prepared solution was added. 2.45 grams of Ammonium
Persulfate (APS) was added in 50 ml of Distilled water to uniformly mix the APS. After
uniform dispersion of APS into the Distilled water it was added slowly into the aniline
solution drop wise using the burette as shown in figure 12(a). After addition of APS, the
solution was stirred for 7 hr. at 700 rpm, the temperature of the solution was maintained by
using ice bath. During stirring, the colour of the solution turns into dark green. The solution
was kept overnight in the refrigerator. Vacuum filtration was carried out to obtain the PANI
from the solution using Whatman 40 filter paper. The sample retained over the filter paper
was dried in the hot oven at 60°C for 2 hours as shown in fig. 14(b).

(a) (b)

Fig. 14. Synthesis of Polyaniline (PANI) (a) showing soln. of APS and distilled water slowly added to aniline
soln. using burette and (b) synthesised Polyaniline (PANI) [MME Department, NIT Srinagar]

5.4 Synthesis of HEA (AlCoCrFeNi)

Metal powders of Co, Cr, Fe, Ni, Al with purities of higher than 99.5 wt.% and particle size
less than 100μm were used as starting materials. The elemental powders were mixed in

22
equiatomic composition and milled in a planetary ball-miller for 30 hrs at 300 rpm. Tungsten
carbide vials and balls were utilized as the milling media with a ball-to-powder mass ratio of
10:1. Toluene acts as the processing controlling agent (PCA) to avoid cold welding as well as
to prevent the alloy from oxidizing. The MA process was monitored by powder extraction at
a regular interval of 10h.

(a) (b)

Fig. 15. Synthesis of HEA (a) Hi-Speed Planetary Ball Mill and (b) synthesised HEA (AlCoCrFeNi) [CRFC
NIT Srinagar]

5.5 Synthesis of rGO - PANI - HEA nanocomposite

To synthesis the nanocomposite, ice bath was used to control the temperature and initially 50
ml of Distilled water was used and in this 4.10 ml of HCL was added. Separately 1 ml of
Aniline, 0.195gm of HEA (AlCoCrFeNi) and 0.195 g of rGO was kept in the beaker in which
the prepared solution was added. 2.45 g of Ammonium Persulfate (APS) was added in 50 ml
of distilled water to uniformly mix the APS. After uniform dispersion of APS into the distilled
water it was added slowly into the aniline solution drop wise using the burette as shown in
figure 16(a). After addition of APS, the solution was stirred for 7 hr. at 700 rpm, the
temperature of the solution was maintained by using ice bath. During stirring, the colour of
the solution turns into dark green. The solution was kept overnight in the refrigerator. Vacuum
filtration was carried out to obtain the nanocomposite from the solution using Whatman 40
filter paper. The sample retained over the filter paper was dried in the hot oven at 60°C for 2
hours. The dried sample was crushed into powder using mortar and pestle.

23
 (a) (b)

Fig. 16 (a) Showing soln. of APS and distilled water slowly added to soln. using burette (b) synthesised
nanocomposite retained over Filter paper [MME Department, NIT Srinagar]

5.6 Preparation of rGO-HEA-PANI-composite slurry and Electrode

To prepare rGO - HEA - PANI – Composite slurry, we use 0.032g HEA, 0.032g rGO, 0.032g
PANI and 0.032g Composite and keep them separately in different containers. Then we have
added 0.004g acetylene black and 0.004g PVDC (Polyvinylidene chloride) in each
containers. Here we use acetylene black to increase conductivity, absorbing ability,
compressibility, elasticity and act as conductive additive whereas PVDC is used as polymer
binder. After adding acetylene black and PVDC we add 2ml N-methyl-2-pyrrolidone which
act as solvent for PVDC and stirred for 2 hrs. After stirring crushing and grinding is done by
using mortar and pestle for 2.5 hrs.

24
 (a) (b) (c)

Fig. 17. (a) sonication of solutions for 2h (b) Swagelok Cell (c) Electrochemical Spectroscopy Setup [MME
Department, NIT Srinagar]

25
 CHAPTER: 6

RESULTS AND DISCUSSION

6.1 XRD Analysis

Figure 18 shows the obtained XRD plot from the pristine Graphite and as-synthesized
GO, rGO, PANI, HEA at 0 hr, HEA at 10hr, HEA at 20hr, HEA at 30hr and Nanocomposite
(rGO + HEA + PANI) . In the case of pure graphite, a strong XRD peak at 2θ = 26.5° and
a slight peak at 2θ = 54.5° were observed specific to the (002) and (004) plane. A
strong characteristic peak of GO (Graphene Oxide) is observed at 2 θ of 1 0 . 3 7 °
which is quite matching with available literature indicating an increase in the
interlayer spacing as apparent by shifting of the peaks towards lower angle. The
increase in d spacing of GO at this peak is calculated as 8.523 Å which is more
than the double of Graphite d spacing calculated as 3.36 Å using Braggs equation
nλ=2dsinθ where λ = 1.5406. The increase in interlayer spacing is due to the
introduction of oxygen containing groups compared with typical graphite which
confirms the expansion of graphite stacked layers. From the XRD plot of rGO shown
in Figure 15 the peak shifted from ~10.37° to ~ 27.26°, with the interlayer spacing of 3.26 Å
confirming the successful removal of oxygen rich group from rGO using Modified Hummers
Method. The increase in the interlayer spacing’s from the pristine graphite also shows the
formation of graphene sheets with successful exfoliation. From the XRD plots of pure PANI
a sharp peak is seen around 25.18° accompanied by other two low intensity peaks with their
position around 20.31° (020) & 15.26° (011) respectively. From XRD patterns of HEA
(AlCoCrFeNi) shown in Figure 15 reveal that one major phase of AlCoCrFeNi HEA is formed
within a milling time of 30 h. The primitive blending powder includes diffraction patterns of
all alloying elements. After 10 h mechanical alloying, the diffraction peaks of the principle
elements can still be observed with a dramatic decrease in intensity. With prolonged milling
time, peak broadening is obvious and some peaks become invisible after 20 hrs of milling. As
the milling time increases to 30 hrs, only the two most intensive peaks of a BCC structure

26
(110) and (200) can be identified, by which is deduced the formation of a simple solid
solution. From the XRD plots of Nanocomposite rGO + HEA + PANI, the presence
of rGO, HEA (AlCoCrFeNi) and PANI peaks are seen which confirms the
composite formation. This is due to the strong electrostatic force of interaction
between graphene sheets, HEA and chains of polyaniline confirming the nano-
composite.

(a)

27
 (b)

Fig. 18. (a) XRD of Graphite and (b) XRD of GO, rGO, PANI, HEA at 0hr, HEA at 10hr, HEA at 20hr, HEA
at 30hr and rGO+PANI+HEA nanocomposite

6.2 ANALYSIS OF HEA & Composite (rGO+PANI+HEA) Microstructures

& Morphology

The microstructure and morphology of the HEA (AlCoCrFeNi) & nanocomposite (rGO +
PANI + HEA) synthesized material analyzed by FE-SEM. The SEM micrographs of
AlCoCrFeNi high entropy alloy after 30 h of milling reveals that the particles size reduces
continuously with the increase in milling time. After 30 hrs of milling, flaky particles are also
observed, and volume fraction of flaky particles continuously increases. Probably, during the

28
mechanical alloying process, continuous deformation, fracturing and cold-welding leads to
the enhanced diffusivity of the elements cold and leading to the formation of HEA alloy. From
the EDAX data we observed that 6.9% Al, 12.1% Cr, 15.8% Fe, 19.2% Co, 8.2% O and 19.3%
Ni is present in HEA (AlCoCrFeNi). The SEM micrographs of Nanocomposite (rGO + PANI
+ HEA) reveals that HEA (AlCoCrFeNi) surface is homogeneously covered with
interconnected networks of PANI spines of PANI and graphene in the composite. The EDAX
data show that 61.4% C, 13.6% N, 18.4% O, 0.6% Al, 1.7% Cr, 1.5% Fe, 1.2% Co, and 1.6%
Ni is present in composite (rGO + PANI+HEA). Following analysis confirms there is no other
element presence except aluminum, cobalt, chromium, iron, nickel, oxygen, nitrogen and
carbon thus confirms the absence of any other impurity present in prepared nanocomposite
(rGO + PANI + HEA) samples. It can be seen that Al, Co, Cr, Fe and Ni elements distributed
evenly in the HEA. EDS mapping also reveals that in very small amount oxygen is also

present that is distributed evenly in the HEA.

(a)

29
C Ni O

Al Cr Fe

30
Co Ni

(b)

Fig. 19. (a) The SEM-EDS elemental mapping of the fabricated AlCoCrFeNi HEA by mechanical alloying (b)
The SEM-EDS elemental mapping of rGO + PANI + HEA composite.

6.3 Raman Spectroscopy

By Raman Spectroscopy Graphene layers and the structural quality can be studied.
Monochromatic radiation of Raman spectroscopy interacts with the molecular vibration of
graphene resulting in a shift in radiation due to scattering. Raman spectra of rGO shown in
figure 18. Here in case of rGO two main peaks are observed which include D and G peaks. D
peak is observed at 1349.93 cm-1 indicating a disorder in sp2 hybridization. G peak is observed
at 1602.75 cm-1 representing lattice vibration. An increase in graphene disorder increases the
ratio ID/IG because of the elastic scattering due to the higher defect intensity. However, when
the carbon structure becomes more amorphous, the ID/IG ratio decreases. These peaks
confirms the reduced graphene oxide formation.

Fig. 18. Raman spectra of rGO.

6.4 Electrochemical measurements

31
For electrochemical analysis, the symmetric supercapacitor was designed as a two-electrode
system. In the construction of symmetrical supercapacitors, the nanocomposite and RGO as
active material, a pair of carbon paper with material deposit act as current collector, Whatman
paper as separators, and 0.1 M H2SO4 as electrolytes were used. Specific capacity was
calculated using the following formulae:

C = ∫ iVdV/μmΔV *2 .eq.(1)

where, ∫ iVdV is generally the area below the CV curve diagram where V and i are potentials
and currents in CV analysis. ΔV is the potential window, m is the mass of active substance
used, and μ is the potential scan rate

Cyclic voltammetry (CV) studies

The CV analysis of electrodes was carried out to examine the potential of each synthesized
material in electrical charge storage. The behavior of these electrodes at various scan rates in
the CV test is one of the most crucial factors in assessing an electrode’s SCs capabilities. The
improved double-layer capacitive affect behavior, which is dependent on the electrical double
layer generated at the electrode solution interface, was shown by the CV curves in Fig. 20(a–
e), which were attained with a scan rate range of 1–100 mV/s. In the prepared electrodes, a
CV with a rectangular form devoid of redox peaks was seen. This demonstrates unequivocally
that there is a significant capacitive response present at the interface between the electrode
material surface and the electrolyte. Additionally, the rectangular form of CV at a high scan
rate suggests that the capacitor has a low internal resistance and high-rate capability

32
Fig. 19. (a) All CV plot ( rGO, HEA, PANI and nanocomposite)

33
Fig. 20 Depicts the CV curve of the different electrodes(PANI/Hea/rGO/Composite)in which Composite encloses a
higher area under the curve than other electrodes and has a higher current response. Further, Composite electrode has
provided a greater specific capacitance (Csp) of about 961F/g, as compared to pure PANI (533F/g), HEA(219F/g),and
RGO (112.84F/g) at 10 mV/s scan rate, measured using Eq(1).The co-doping of HEA with RGO has created a
synergistic impact in capacitance. The electrochemical capacitance behavior of all grown electrodes was also
evaluated at varying scan rates, and obtained cyclic voltammogram are illustrated in Fig. 13(b-e) and calculated
specific capacitances from Eq.(1).

Galvanostatic charge discharge (GCD)

Galvanostatic charging-discharging (GCD) is the utmost precise technique for capacity

measurements. The GCD techniques have contrived the specific capacity and sustainability of all
the samples of HEA/PANI/RGO/COMPOSITE electrodes. Commonly, two dissimilar types of
discharging performance are there with linear and non-linear shapes. Rectilinear state signifies the
storing of charge in the cathode centered on the adsorption-desorption response. Then non-linear
state designates the pseudo or battery type performance of the electrodes. In the current study, the
non-linear discharging bend was detected, which specifies the existence of reduction and oxidation
(redox) reaction in the synthesized material. It also strongly agrees with the results of cyclic
voltammetry. GCD technique is a very acceptable practice for calculating the rate capability and
capacity of the electroactive synthesized material. This study has been done to auxiliary explore
the electrochemical behavior of the assembled working electrodes.

34
 (a) (b)

(b) (d)

Fig. 21 (a) rGO GCD graph (b) Composite GCD graph (c) HEA AlCoCrFeNi GCD graph and (d) PANI GCD graph

The specific capacitance (Cdsp), energy density (E), and power density (P) measurements from
GCD plots were carried out using the following equations,

C= ( I* T/ ΔV *m)*2 .eq(2)

The specific capacitance measured from Eq(2), Capacitance at a current of 0.0003 A are 95, 51.04,
266.76, 303.125, for pure HEA, RGO, PANI, COMPOSITE electrodes, respectively. The high
value of Cdsp for COMPOSITE electrode is ascribed the extended discharging time than all other
doped and co doped electrodes. From the results, it is noticeably observed that the discharging
time and specific capacitance decrease at higher current density for all fabricated electrodes. This
might be because interaction among electrolytes and electrodes most probably occurs at the
surface, which can lead to the fastest discharging time.

35
 CHAPTER: 7

CONCLUSION

• GO was prepared by Modified Hummers’ method and rGO was prepared with the aid of
hydrazine hydrate successfully. The characterization results indicate that the layer spacing
of graphene oxide was longer than that of graphite.

• HEA (AlCoCrFeNi) was synthesised using Hi-Speed Planetary Ball Mill. The
characterization results indicate the formation of HEA.

• XRD, Raman Spectroscopy & SEM Analysis of GO, rGO, PANI, HEA (AlCoCrFeNi)
and rGO+HEA+PANI confirmed the successful nanocomposite formation.

• When used as a free electrode for supercapacitor, the Composite electrode has provided a
greater specific capacitance (Csp) of about 961F/g, as compared to pure PANI (533F/g),
HEA (219F/g), and RGO (112.84F/g) at 10 mV/s. Capacitance at a current of 0.0003 A
are 95, 51.04, 266.76, 303.125, for pure HEA, RGO, PANI, COMPOSITE electrodes,
respectively.

• The high value of Csp for composite electrode is ascribed the extended discharging time
than all other doped and co doped electrodes. From the results, it is noticeably observed
that the discharging time and specific capacitance decrease at higher current density for all
fabricated electrodes. This might be because interaction among electrolytes and electrodes
most probably occurs at the surface, which can lead to the fastest discharging time.

36
 CHAPTER: 8

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