Fabrication of Electrode Material PbAl2O4 via Simple Sol-Gel Method for

Supercapacitor Applications

Master of Physics

Submitted by

Muhammad Adnan

Roll No; 09

2022-2024

Master of Physics

Gomel University Dera Ismail Khan

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 CERTIFICATE

It is verified that the research included in this thesis was conducted, entitled has been carried out
by Muhammad Adnan S/O Muhammad Ramzan Roll No.09, Session (2022-2024), MS
Physics, Gomel University Dera Ismail khan Ghazi University. The report is submitted in partial
requirement for the award of MS Physics.

Research Supervisor Director

Professor Dr. Hasnain Qaisrani

Gomel University Dera Ismail Khan.

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 ACKNOWLEDGEMENT
In the name of Allah (SWT), the almighty, the most compassionate, the most giving, and
deserving of all adoration. All praise is due to the almighty Allah (SWT), who illuminates our
paths and leads me while I'm lost in confusion. Countless salutations salutations to the
fountainhead of wisdom, our beloved Prophet Muhammad (S.A.W.), who embodies compassion
and leadership for all people in all spheres of existence.
I would like to take this opportunity to convey my sincere gratitude to my esteemed
supervisor, Professor Dr. Hasnain Qaisrani Sahib, for her unwavering support, kind guidance,
thoughtful criticism, and helpful suggestions at every turn that enabled me to finish this thesis. I
cannot be able to thanks her for her supervision. I vital offer my warm gratitude to her for all her
guidance from start till the end of the thesis. I would want to express my profound gratitude to
Professor Dr. Hasnain Qaisrani, for providing me with this opportunity and for making the
arrangements that are in place. In his capacity as a supervisor, he gave me access to all the
resources I needed and made the study process very cooperative and enjoyable. Finally, but just
as importantly, I want to express how grateful I am to my parents for their financial support and
encouragement as I finished my MS in Physics.
I also want to thank all of my wonderful professors and teachers, who inspire me to be a wise
and experienced person and all the practical staff of Physics Department Gomel University Dera
Ismail Khan for their support and direction in our experimental work.

Muhammad Adnan

 Table of Contents
 Abstract.............................................................................................................................................7
 Introduction.......................................................................................................................................8
 1.1...........................................................................................................................................Energy:
8
 1.1.1 Energy Crises:........................................................................................................................8

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 1.1.2 Causes of Energy Crises:.......................................................................................................9
 1.2........................................................................................................Renewable Source of Energy;
10
 1.2.1 Solar Energy;.......................................................................................................................10
 1.2.2 Solar Cells............................................................................................................................11
 1.2.3 Wind Energy:.......................................................................................................................13
 1.2.4 Water Energy:......................................................................................................................14
 1.2.5 Tidal power:.........................................................................................................................15
 1.3.................................................................................................................Energy Storage Device:
17
 1.3.1 Batteries:..............................................................................................................................17
 1.3.2 Cells:....................................................................................................................................17
 1.3.3 Capacitors:...........................................................................................................................17
 1.4.............................................................................................................................Supercapacitors:
18
 1.4.1 Advantage of Supercapacitor:..............................................................................................21
 2.............................................................................................................................Literature Review
........................................................................................................................................................22
 3............................................................................................................................EXPERIMENTAL
........................................................................................................................................................27
 3.1..........................................................................................................................List of Apparatus:
28
 3.1.1 Spatula:................................................................................................................................28
 3.1.2 Beaker:.................................................................................................................................29
 3.1.3 Measuring Balance:.............................................................................................................29
 3.1.4 Magnetic Stirrer and Hot Plate:...........................................................................................30
 3.1.5 Crucible:...............................................................................................................................30
 3.1.6 Oven:....................................................................................................................................31
 3.1.7 Mortar Pestle:.......................................................................................................................31
 1.......................................................................................................................Hydrothermal Method
32
 2...................................................................................................................Co-precipitation Method
32
 3.................................................................................................................................Sol-gel Method
32

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  4............................................................................................................................Solid State Method
32
 3.2..................................................................................................................Hydrothermal Method:
32
 3.3............................................................................................................................Sol-Gel Method:
33
 3.4...............................................................................................................Co-precipitation Method:
34
 3.5.......................................................................................................................Solid State Method:
35
 4.......................................................................................................................Result and Discussion
........................................................................................................................................................36
 4.1..................................................................................................................Preparation of PbAl2O4
36
 4.2.........................................................................................................Electrochemical Techniques:
37
 4.2.1 Cyclic Voltammetry:............................................................................................................37
 4.2.2 Electrochemical Impedance Spectroscopy:.........................................................................39
 4.2.3 Galvanostatic Charge Discharge:.........................................................................................41
 4.2.4 Chronoamperometry:...........................................................................................................43

Table of Figures

Figure 1. 1 Energy Crises..............................................................................................................................9

Figure 1. 2 Causes of Energy Crises...........................................................................................................10
Figure 1. 3 Solar Energy.............................................................................................................................11
Figure 1. 4 Working of Solar Cells.............................................................................................................12
Figure 1. 5 Wind Energy.............................................................................................................................13

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Figure 1. 6 Water Energy............................................................................................................................15
Figure 1. 7 Tidal Power...............................................................................................................................16
Figure 1. 8 Energy Storage Devices............................................................................................................18
Figure 1. 9 Super Capacitor........................................................................................................................19
Figure 1. 10 For Super Capacitor................................................................................................................20

Figure 3. 1 Spatula......................................................................................................................................28
Figure 3. 2 Beaker.......................................................................................................................................29
Figure 3. 3 Measuring Balance...................................................................................................................29
Figure 3. 4 Magnetic Stirrer & Hot Plate....................................................................................................30
Figure 3. 5 Crucible....................................................................................................................................30
Figure 3. 6 Oven..........................................................................................................................................31
Figure 3. 7 Mortar Pestle.............................................................................................................................31

Figure 4. 1 Cyclic Voltammetry.................................................................................................................37

Figure 4. 2 Specific Capacitance vs Scan Rate...........................................................................................38
Figure 4. 4 Electrochemical Impedance Spectroscopy by fit......................................................................39
Figure 4. 5 Galvanostatic Charge Discharge..............................................................................................41

Abstract
The world energy demand increasing, and the storage of energy is a big problem. The
supercapacitors are the best known devices to store the energy because of their high energy
density (Ed) and power density (Pd). Here, in this study, we fabricate the electrode material

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(PbAl2O4) for SCs via using the sol-gel method. The synthesized PbAl 2O4 material was tested by
various physical and electrochemical technique. The electrochemical analysis was performed on
three-electrode method one was usable electrode, the other counter electrode and character
electrode in a basic (3M KOH) as electrolyte. The prepared material result show high specific
capacitance (852.84 F/g) at a current density (Cd) of 1 A/g, power density (320.17 (KW Kg-1)
and energy density (48.54 Wh K/g). All these results demonstrate that the electrode material is
suitable for SCs and other electronic devices.

Introduction
1.1 Energy:

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The energy is said to be the ability of to do work. Modern human civilization is made possible by
the discovery of the ability to convert energy from one form into others then use it to fulfil tasks.
Energy is utilized for a many activities, walking and including biking, driving vehicles on roads
as well as through water, forming ice in the freezer, heating food on stoves, light our offices and
homes, launching astronauts and producing commodities into the space [1]. Energy is found in
several forms:

 Gravitational
 Chemical
 Heat
 Electrical
 Light
 Motion

1.1.1 Energy Crises:

Any significant issue that makes it tough for a region to meet its energy supply needs is known
as an energy crisis or an energy shortage. This term is frequently used to indicate the situation
where there is a shortage of energy sources available for use at a certain time and location,
especially when referring to energy systems as a source of fuel [2].

The fast increase of energy consumption as well as the widespread utilization of fossil fuels have
led to alarming levels of environmental pollution. Both climate change and pollution pose
serious threats to environmental protection. In an effort to address this issue, researchers are
working on creating clean and renewable energy sources. However, all of these sources are
weather-dependent, including solar, wind, and tidal power [3]. Figure 1.1 shows that the energy
crisis is symbolized by a hand holding a light bulb, accompanied by an icon representing energy
resources, along with a growing data chart displaying electricity consumption, alternative energy
sources, and sustainability.

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 Figure 1. 1 Energy Crises

1.1.2 Causes of Energy Crises:

 A rise in Population.
 Limited availability of renewable resources.
 Distribution of resources are poorly organized.
 A century old structures
 The Energy wastage.
 The price of fossil fuels has increased due to an increase in demand.
Some contend describes that unbalanced supply and demand is the tax rises, government
takeovers of energy companies, and business regulations [4].The figure 1.2 shows that one of the
key reasons for energy problems is the expanding population.

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 Figure 1. 2 Causes of Energy Crises

Energy from renewable sources is the only answer to the energy crisis we are now facing.

1.2 Renewable Source of Energy;

1.2.1 Solar Energy;

Energy sources that are constantly replenished are known as renewable energy sources because
they will never be depleted. [5]. Solar power, hydropower, biomass, wind power, and geothermal
energy are some examples of renewable energy sources.

Renewable energy is the general term for all solar energy that humans can use directly or
indirectly. It is recognized as eco-friendly because it does not produce greenhouse gases.

Flat-plate collectors were the most famous devices for gaining solar energy and converted to the
electrical power. Solar ponds, seawater reservoirs built to store solar energy that are another
means of converting in thermal energy. That specifically designed in solar ovens, which typically
emit sunlight from the broad region to a centre point, food may also be cooked utilizing solar
energy. Solar energy is a small investment that will yield long-term benefits for energy-efficient

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businesses and homes.The solar panels can also convert sun energy directly into electrical power
[6].

Figure 1.3 show that the sun's light is converted into electrical energy using photovoltaic solar
panels installed on the roof.

Figure 1. 3 Solar Energy

1.2.2 Solar Cells.

The term "solar energy" means to energy that created through the sun. According to
technological devices, there are several ways to utilize this numerous resource. It is recognized
as a green technology since it doesn't emit greenhouse gases. A solar cell was made via
depositing a few thin sheets of the PV material onto the supporting materials, metal, like as glass,

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or plastic [7]. The most common types of thin-film PV semiconductor available today are
cadmium telluride.

1.2.2.1 Working of Solar Cells.

The basic functioning of a solar cell was comparable to conduction in a silicon-based

semiconductor [8]. The part of the surface that is exposed to the sunlight is the dark one, as seen
in the figure 1.5 image. Electromagnetic radiation stimulates the electrons onto the cell's surface,
causing them to move from a specific energy level to another and leave holes.

Figure 1. 4 Working of Solar Cells

The electrons are the negative carriers of charges, whereas these holes are the positive charge
carriers, neither electrons nor holes are responsible for producing electrical charges. They only
move the bills. EM radiation is transformed into electrical energy in this way [9]. The main
components of solar cells contain semiconductors, with selenium and silicon being the most
popular.

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1.2.3 Wind Energy:
Wind energy was technique of utilizing to produce the electrical energy. Wind turbines
converted of the kinetic energy (K.E) of wind to the mechanical power. The mechanical power
may be applied to converted to the electricity for specific tasks using a generator [10].

The power of wind was generated via converting the K.E of air that change into electrical
energy. Current wind turbines were propelled through wind that converts K.E to the energy of
rotation by the rotors.

The threat caused by environmental change has prompted countries from around the world to
make investments in renewable energy. One of the several renewable energy sources which was
growing the fastest is wind energy [11].

Figure 1. 5 Wind Energy

Wind power was one of the most frequently utilized renewable source of energy in the country.

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Wind energy presently accounts for almost 9% of all energy generated by the US, and it has
great growth potential. But while determining how we will power our future, it's essential to
consider all characteristics of an energy source.

1.2.4 Water Energy:

BF, a French engineer that was developed the first hydroelectric turbine. Hydropower, also
known as hydroelectric energy that was produced by using the dam or another structures that can
converted of the natural flow of a river [12]. Wind energy can be transformed by wind turbines
into the electrical power that powers used in our houses and places of business. They can be
grouped together to create a wind power plant or they can exist independently, serving only one
or a very small number of residences or establishments.

Water movement is the source of hydroelectric electricity. The word hydro is a Greek word that
derived from the water.

Here, figure 1.6 shows that how they work as well as why they were so significant for the
advance of energy.

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 Figure 1. 6 Water Energy

Hydroelectric energy has been used for several thousand years. The Romans invented turbines,
which are wheels that rotate by flowing water. Instead of being utilized to produce energy,
Roman turbine are utilized to mill wheat into flour and breads.

Wind turbines typically come with either white or an extremely light version of grey to be as
unobtrusive as possible [13]. There has been discussion about if they should occasionally be
painted another color to better mix in with the surroundings, usually a shade of green.

The Federal Aviation Administration in the United States demands that turbines be white or off-

white, although some governments also demand extra markings, usually on the tips of the blades.

1.2.5 Tidal power:

Utilizing a variety of techniques, tidal energy was produced via transforming energy through the
tides into the useable forms of energy that primarily electricity.

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Even though it is not currently widely used, tidal energy having potential to produce electricity in
near future. It is easy to predict tides than the wind or the sun [14]. Because of its relative
expensive price and scarcity of locations with sufficient tidal ranges or fluid velocities, tidal
energy represents one of the sources of clean energy that used to have restricted access. But a
number of recent advances and modifications, both in development and turbine construction,
imply that the overall availability of tidal strength may be far greater than earlier assuming and
that financial as well as environmental expenses could decrease to comparable levels.

Figure 1. 7 Tidal Power

The concept of hydroelectric power is comparable to that of wind power, which uses its
energy to propel a turbine's wheels [15]. Hydroelectric power generates electricity by using the

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mechanical energy provided by the natural flow of water to power turbines. For energy, the
water runs continually. Water receives the kinetic energy from gravity that it needs to flow.

1.3 Energy Storage Device:

A storage system or battery was a term that used to describe an instrument that stores energy.
There were several different types of energy, radiation including,
chemical, heat, kinetic, gravitational, latent, electricity, and potential [16].
The various form of storage devices are like as capacitors, cells and batteries.

1.3.1 Batteries:
A battery was a device that converted chemical energy consist in the active parts direct into
the electrical energy using a redox, or electrochemical oxidation-reduction cycle [17]. In this
type of the reaction, electrons were transferred from a material into another utilizing an
electric circuit.
Here were a few everyday applications of batteries. Batteries were found in many of the
everyday goods we used. Batteries were utilized to the power a kind of gadgets, such as
remote controls, aids, torches, wall clocks, scales, spotlights, hearing, and more.
1.3.2 Cells:
A device that changed the chemical energy into the electrical power was known as an electric
cell [18]. It consists of two metallic terminals, one labeled as positive (+) and the other as
negative (-).Electric current flows through an electrical device when these two terminals are
connected.

1.3.3 Capacitors:
Contrast to a batteries, a capacitor was a part of a circuit that uses the potential difference created
by particles of charge distributed between (typically two) plates for storing electrical energy. A
capacitor can lose all of its stored energy in a few of minutes and charge more quickly than a
battery [19].

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 Figure 1. 8 Energy Storage Devices

1.4 Supercapacitors:

A huge amount of charged can be stored in an electrical device called a supercapacitor. These
kinds of capacitors are also referred to as ultracapacitors [20].

Three categories of SCs are recognized:

 Pseudo-capacitors. By transferring electron charges from electrode to electrolytes

pseudo-capacitors stored energy from electricity. Redox can accomplish this.

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  Hybrid capacitors. The pseudo-capacitor and double layer capacitor techniques are used
to create the hybrid capacitors. Both pseudo capacitance and double layer capacitance are
accomplished in hybrid capacitors.
 Electrostatic double-layer capacitors. The components of a double layer capacitor are a
separator, an electrolyte, and two electrodes. A combination of negative and positive ions
saturated in water called the electrolyte [21]. A separator separates the two electrodes.

Recent developments in the field led to the development of the supercapacitor as a workable
substitute. In supercapacitors, thin electrodes and dielectrics with a high area of surface to
the volume ratio are used [22]. This enables them to have a capacitance that is higher than what
is permitted by traditional capacitor equations. These qualities cause them to have higher energy
and power densities than batteries as well as conventional capacitors [23].

Figure 1. 9 Super Capacitor

Dual layer capacitors were a subset of SC, hybrid capacitor, and pseudo capacitors established on
how they store charge [24]. Pseudo capacitors use electrochemical charge storage, while hybrid

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capacitors use both. Supercapacitors work well with electronics that demand large currents for
limited periods of time since they are frequently pulse current devices. In order to use these
materials in a wider range of applications, researchers are working to boost the energy density of
these materials. The electrolyte, the voltage, and the electrode materials all have an impact on
how well a supercapacitor performs. The majority of research, however, focuses on enhancing
electrode materials. This study investigates how supercapacitors store electrode materials like
carbon, conducting polymers and metal oxide [25].

Figure 1. 10 For Super Capacitor

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Usually a rectangle or a cylinder-shaped supercapacitor is produced. The layers are layered in a
rectangular container or an aluminium can, as indicated in figure 1.11.

1.4.1 Advantage of Supercapacitor:

 When compared to a normal capacitor, it delivers a high the density of energy and high
power density.
 High capacitance is available, ranging from (2 mF to >10,003F).
 It has quick charged capabilities.
 From -40°C to 70°C, it provides exceptional low temperature efficiency.
 It has a longer lifespan and provides longer service. It can be repeated millions of times
and has a virtually limitless cycle life.
 It gives improved efficiency reliability.
 It decreases the battery's magnitude, cost, and mass in turn.
 Supercapacitors comply with environmental regulations. So they are environmentally
friendly.
 Using regenerative braking, automobiles and electric mass transit vehicles are able to
recover the thermal energy that the otherwise would have been lost during braking.
 Because batteries encapsulate an enormous amount of energy in a compact area, they can
be used continuously, while recharging them can take a long time. Electrochemical
capacitors known as SC are utilized for quick transfer of power and battery charging.
 Reduce the quantity of room you require.
 Suppress the noise that the pulse current produces.
 It aids in distributing the load when used in combination with a battery. When combined
with power sources, these devices can store and distribute energy.

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 2 Literature Review

Jinhui Xu et al, fabricated NiO/rGO electrode material via hydrothermal technique for SCs.
SEM, XRD, FTIR, and Raman were utilized to analyze the samples' microscopic phase structure
and morphology. To investigate the electrochemical characteristics and cycle efficiency of
the composite electrode NiO/rGO, GCD, CV, and the AC impedance were used. The findings
demonstrate that the addition of graphene in nickel oxide then a significant improves in the
reversibility was observed in the electrode material. A continuous networks and more active
places for redox reactions were provided by the unique structure of graphene. When the 0.5 A g-1
Cd was applied by utilized 6 M KOH electrolyte then the Cs of NiO/rGO composite was 170.9
F/g, of a 5 A/g at 2000 cycles, the measured loss in capacitance was 20% [26].

Young-Seok Lee et al, fabricated CoCu2O4 electrode material using the hydrothermal technique
for SCs. The CoCu2O4 Nano flowers exhibit a wide surface area, increased ion accessibility, and
accelerated electron flow speed, enhancing their electrochemical activities. The current CoCu 2O4
Nano flower electrode represented the high capacitance of 353.84 C/g at 2 A/g of an aqueous
electrolyte, 96.9% of the initial capability was retained at 3000 lengthy and continuous the
charging and discharging cycles. The increased surface area and improved ion transport are
primarily responsible for the CoCu2O4 Nano flowers' super-active electrical capabilities, making
them a potential option for utilize as an electrode material in super capacitors for energy storage
[27].

Hongmei Wei et al, prepared of NiMn2O4 metal using the hydrothermal method for
supercapacitor. Using a Cd of 1 A/g, NiMn2O4 outperformed Mn3O4 in a system with three
electrodes shows larger Cs (663.1 F /g and 371.2 F/g in various electrolytes) and superior cycling
stability (96% Cr after 1000 cycles). Their improved electrochemical properties were caused by
the new microstructure, which was produced directly to the conductive substrate and supplied
enough sites of activity for redox reactions [28].

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Veeman Sannasi et al, fabricated ZnMn2O4 of electrode material by hydrothermal method for
supercapacitor. Utilizing a three-electrode setup, the electrochemical characteristics of the
manufactured composite of the materials were examined, and they reveal a pseudo capacitance
nature. GCD experiments reveal that the composite material has a high Cs of 380 F/g and 0.5
A/g. At a Cd of 3 A/g at 2000 cycles, the produced ZnMn2O4/Mn2O3 composite exhibits
outstanding stability during cycling at 92% of the original Cs. The electrochemical analyses of
composite suggest that ZnMn2O4/Mn2O3 may be applied for SCs applications [29].

Ghulam Nabi et al, prepared CoFe2O4 via hydrothermal technique for SCs. The fabricated
CoFe2O4 exhibits a higher structure and enriched morphology. Electrochemical work of
CexCoFe2-xO4 (x = 0, 0.4, and 0.6) electrodes were conducted with the assistance of CV, EIS, and
GCD of the 1 M KOH electrolyte. The longest cycling life along with the maximum Cs of
936.84 F g-1 were achieved with the capacitance retention of 81.9% after 4000 cycles. The
manufactured Ce 0.48 CoFe 1.518 electrode is a strong candidates for SCs applications [30].

Chanchal Mondal et al, synthesized MWCNT/Mn 3O4 material for using hydrothermal. The
electrochemical analyses demonstrate of suitability of the prepared MWCNT/Mn 3O4 composite
material. It’s Cs, which was 1.5 times greater than the Cs (315 F g -1) of bare Mn3O4 nanoparticles
at a scan rate 3 mV s -1, is 439 F g-1 at 3 mV s-1. MWCNT/Mn3O4 exhibits excellent rate
performance, superb 99% retention after 1000 consecutive cycles, and improved power density
and energy density. The capacitance performance of hybrid electrode significantly was
improved due to the synergistic interaction between the conducting MWCNT and the
nanoparticle pseudo capacitor Mn3O4.This effective composite could be advantageous for super
capacitor applications [31].

M. Jayachandran et al, fabricated MnO2 for their electrode material by hydrothermal technique
for SCs. Powder XRD and HR-TEM investigations were used to examine the morphological and
structural quality of the active materials. Electrochemical measurements demonstrated that in a
combined electrolyte of 0.8 M KOH as well as 1.1 M Na 2SO4, the MnO2 Nano rods exhibited a
Cs of 575 F/g at a Cd of 2 A/g. At a Cd of 9 A/g, a Columbic performance of approximately 81%

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was also observed. Additionally, at 10,000 cycles in a mixed electrolyte of 1.1 M Na 2SO4 and 0.5
M KOH, the Columbic retention (Cr) was determined to be 81%. This study demonstrated the
high efficiency of MnO2 Nano rod material for electrodes in the mixed electrolyte solution. It
was discovered that this electrode-electrolyte combination holds the most promise for
supercapacitor applications [32].

F.F.Alharbi et al, the fabricated MnCr 2O4 electrode material via electrospining technique for
supercapacitor. XRD, SEM, and electrochemically study, in that order, provided evidence of the
structural, electrochemical performance, and morphology. The synthetic material has cubic form
morphologies, average particle sizes of 58 nm, and crystallite sizes of 51 nm. The prepared
MnCr2O4 nanostructures electrodes achieves an excellent specific energy value 185 Wh k/g and
the specific power level 17.41 W k/g at low current density 0.2 A/g.They also exhibit a Cs value
1649 F/g. The prepared electrode demonstrates remarkable stability during cycling, retaining
78% of its Cr content over 1000 charging and discharging cycles [33].

Sarah Malik et al, prepared MnNiCo material by using hydrothermal process for
SCs. Morphological as well as resources were investigated. As-fabricated MNC-GNP composite
demonstrated best electrochemical resources owing to higher porosity offered via graphene Nano
platelets as well as synergistic effects fabricated through individual components of composite.
When put through electrochemical testing, MNC-GNP showed an improved Cs of 606 m Ah g-1,
which is greater than MNC's 245 m Ah g-1 at Cd of 2.1 mV/s. Additionally, the GCD shown that
MNC-GNP had a longer charge-discharge duration than its equivalent. Additionally, MNC-GNP
has demonstrated charge stability and 98.9% retention over 1000 cycles. Because of its improved
electrochemical characteristics, the synthesized composite proves to be a
useful SCs for electrode material [34].

Lina Chen et al, fabricated LiMn2O4 by high-powered ball milling technique for SCs. The use of
ball milling commercialized LiMn2O4 nanoparticles enhance electrochemical efficiency,
specifically ultrahigh rate capacity, when used as the cathode for aquatic hybrid SCs. The
exceptional results are attributed to the nanotechnology-enabled even dispersion of LiMn 2O4

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throughout the matrix of conducting carbon. The energy density of the integrated LiMn 2O4 as
well as Super P composite, in conjunction with active graphene, in the hybrid SCs, may reach
over 21.49 Wh kg-1, 293.20 W k/g and 14 Wh kg -1 at 5203 W k/g. Additionally, the hybrid
devices exhibit outstanding cycling efficiency, 86% retaining of primarily capacitance even at
4600 cycles [35].

Sathish kumar Chinnapaiyan v et al, fabricated CoAl 2O4 using technique based on hydrothermal
for SCs. The investigation shows that the electrochemical properties of the oxide of bimetallic
CoAl2O4 tailored their behavior by decorating the carbon Nano fibers with it. The charge
capacity for storage of the electrochemically activated CoAl 2O4/CNFs was 2.9 times more than
that of CoAl2O4. At a uniform supplied of 1.3 A/g in 1 M KOH, CoAl2O4/CNFs had Cs 129 C g-
1
. The CoAl2O4/CNFs electrode-fabricated asymmetric structure shown excellent Ed of 21 Wh
k/g as well as power density exceeding 3000 W k/g. The sustainability for the CoAl2O 4/CNFs
electrode was closely scrutinized, and it has a high Columbic performance of 93% as well as the
rate of Cr 96%.The sensor has a good level of selectivity and stability, and can be utilized to
find LUT in diverse samples that are real [36].

Rubia Shafique et al, fabricated CuCr2O4 of material by co-precipitation process of SCs. The
prepared CuCr2O4 has higher structure and enrich morphology. Through the simple fabrication
of the MXene/CuCr2O4 Nano composite utilizing the technique of co-precipitation, this research
inspires the development of Nano-electrode materials with the highest possible conductivity and
stability. The determined crystallite sizes Ti3C2Tx/CuCr2O4 was 22.1 nm, 27.9 nm, and 7.9 nm,
respectively, while sandwich-like morphology having a normal size of grain 1.48 nm [37].

Yong-PingGao Yong-PingGao et al, prepared MgAl2O4 using facile method for SCs. The
ineluctable dispersion and poor natural conductance of MgAl 2O4 material were improved, and a
composite made of MgAl2O4 with rGO that was produced using an easy process has an enormous
surface area and improved conductivity. Its unique structure can effect MgAl 2O4 formation along

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with rGO reorganizing and accelerate the reversible redox processes. The Cs of the
MgAl2O4/rGO composite was 535.8 F g-1 at 1 A g-1 and it also retains 98.6% capacity at 1000
cycles at 5 Ag-1. Utilizing activated carbon based material as well as an MgAl 2O4/rGO
composite, an asymmetrical supercapacitor was created. A maximum power density of 400 kW
kg-1, and 15.7 Wh kg-1 was achieved. Furthermore, this apparatus has successfully powered an
LED, representing its potential use in the energy storage [38].

Le Xu et al, synthesized ZnCo 2O4 of material using facile hydrothermal process for SCs. By
simply adjusting the temperature, the morphology for the substances can easily adjusted
nanowires to Nano belts. The created ZnCo 2O4 nanostructures were utilized as electrode material
in SCs due to their superior fluid nanostructure and easy ion transport. They demonstrate
noticeable pseudo capacitive efficiency with a high Cs of 775.8 F g-1 at 1.2 A g-1 and excellent
cycle stability (85.3% Cr at 2.9 A g-1).Furthermore, a high-voltage asymmetrical supercapacitor
that uses a ZnCo2O4 anode and a graphene oxide cathode, reduced by freezing, displays
outstanding electrochemical characteristics and an ultrahigh power density (83.26 Wh kg -1 at 0.8
kW kg-1), showing well promised for practical use in electrochemical devices [39].

Saad G. Mohamed et al, prepared FeCo2O4 by facile solve-thermal technique for SCs. The
material, as it has been created, possesses a 2D Nano sheet shape, which is expected to offer
superior electronic transport compared to 0-dimensional nanomaterials. FeCo 2O4 Nano sheets
were solved as fabricated material for SCs. When applied on a Ni foam substrate, the material
performed exceptionally well electrochemically in its as-prepared state. It exhibited a
capacitance (Cs) measurement of 854.1 F g-1, at 6 A g-1 as well as impressive cycling stability,
with 89.1% Cr stable over 3000 cycles, demonstrating excellent charge storage capability.
Additionally, it showed enhanced rate capability (74%) when tested at current densities ranging
from 6 to 26 A g-1. The outstanding electrochemical performance FeCo 2O4 Nano sheets can
attributed to their significant porosity, high conductivity, and rapid electron/ion transport [40].

Hong-Wei Tang et al, fabricated NaCo2O4 of electrode material via solid-state reaction process
for SCs. The hexagonal layer structure of the fabricated NaCo 2O4 has been determined using

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XRD analysis. The electrochemical efficiency of the NaCo 2O4 electrode was examined through
the use of NaOH solution with cyclic voltammetry. The findings demonstrate that at a mass-
balanced current of 52 mA g-1, NaCo2O4 electrode's capacitance (Cs) was 335 F g -1 across a
voltage range between 0.16 to 0.67 V. NaCo 2O4 also displays excellent stability and cycling
efficiency in a supercapacitor substance [41].

Surjit Sahoo et al, synthesized MnCo2O4 using a facile hydrothermal method for a supercapacitor
applications. The crystal structure as well as morphology of the substances were investigated
utilizing XRD, energy dispersive X-ray analysis, and three electrodes system was used in a 3 M
KOH solution to study the efficiency of MCO Nano sheets as supercapacitors. The binder-free
electrode exhibited exceptional cyclic stability after more than 10,000 cycles of charging and
discharging, with a higher Cs of 295 F g -1 at 1.3 mV s-1. The obtained energy density for MCO
Nano sheets was 11.124 Wh kg-1, as well as the power density was 5.5 kW kg -1, respectively
[42].

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 3 EXPERIMENTAL Table 1

Sr. No Chemical Chemical Molecular Company M.p (°C) Purity

Name Formula Weight Name B.p (°C) (%)
(g mol -1)
1 Led Nitrate Pb(NO3)2 331.2 Creosol 470 99
Production 83
2 Aluminum Al(NO3)2 164.9 Ottokemi 66 98
Nitrate 135
3 Citric Acid C₆H₈O₇ 192.1 Louis 153 99.9
Francois 310
4 Ethylene (CH2OH)2 62.0 Sigma -12.9 95
glycol Aldrich 197.3

5 Ammonia NH4OH 35.0 Quali-Tech 32 28-30

Solution 100

6 DI Water H2O 18.0 Lovespa 0.00 99

100

3.1 List of Apparatus:

 Spatula
 Beaker
 Measuring Balance
 Magnetic Stirrer
 Crucible
 Oven
 Mortar Pestle

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3.1.1 Spatula:
A flat, flexible blade, broad, known as a spatula was used to lift, spread, and mix materials such
as plaster, medications, foods and paints, as shown in figure 3.1.

Figure 3. 1 Spatula

3.1.2 Beaker:
A beaker was a plastic conical vessel or glass that was used to hold the liquids in itself. . It was a
versatile piece of equipment that can be used for pouring liquids into the beaker. Beakers come
in a variety of sizes, ranging from just 5 milliliter to many liters, as shown in Figure 3.2.

Figure 3. 2 Beaker

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3.1.3 Measuring Balance:
A scale was a mass-measuring instrument, and it was also known by other names such as weight
balances, mass scales, mass balances, and weight scales. Other terms used to refer to this type of
equipment, as shown in Figure 3.3, include pan balances, force-measuring scales, and
mechanical balances, as well as symbolism.

Figure 3. 3 Measuring Balance

3.1.4 Magnetic Stirrer and Hot Plate:

A magnetic stirrer and hot plate was a laboratory apparatus that was a revolving magnetic field
generator with hot plate. This device was used to make a stir bar spin rapidly, immerse it in a
liquid, or mix a solution, as shown in figure 3.4.

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 Figure 3. 4 Magnetic Stirrer & Hot Plate
3.1.5 Crucible:
Crucibles, which have been used since the beginning of time as an instrument for analyzing
metals, were most likely named after the Latin term crux, which means "cross" or "trial." Current
crucibles can range from smaller laboratory equipment used for extreme temperatures chemical
processes and analysis to enormous industrial jars used for calcining and melting, as shown in
figure 3.5.

Figure 3. 5 Crucible
3.1.6 Oven:
A laboratory oven was employed for high-volume heating applications. This laboratory
apparatus maintains a consistent temperature throughout the entire chamber, which was required
for annealing, being dried, sterilization, and various other industrial lab operations, as shown in
figure 3.6.

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 Figure 3. 6 Oven
3.1.7 Mortar Pestle:
To crush solid chemical into small bits or grind solid into a fine powder, used a pestle and
mortar, which are pieces of chemistry equipment. This facilitates the dissolution of particles in
solvents. A pestle and mortar chemical set consist of two components. The pestle was a club-
shaped tool, as shown in figure 3.5, used for crushing.

Figure 3. 7 Mortar Pestle

The nanomaterial electrodes can be prepared using these four fundamental method.
1. Hydrothermal Method
2. Co-precipitation Method
3. Sol-gel Method
4. Solid State Method
Here is a description of each of these techniques.

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3.2 Hydrothermal Method:

Hydrothermal procedures, commonly referred to as "hydrothermal methods," may crystallize

chemical substances at extreme temperatures as well as elevated vapor pressures. The term
"hydrothermal" has its origins in geology. The size and shape of nanostructured substances were
changed by cooling and heating them in water. The hydrothermal method, was a dry chemical
technique that was used to characterize materials prior to their usage in supercapacitor devices.
The flowchart diagram of hydrothermal method as shown in figure 3.8.

Figure 3. 8 Hydrothermal Method

3.3 Sol-Gel Method:

The sol-gel method was considered a practical approach for modifying substrate surfaces. It was
an innovative application of an outdated technique, being used to create new materials. This
method can simplify the tracking of the entire chemical process leading to the formation of
solids. Molecule precursor mixtures were blended to create uniform multi-component structures,
especially uniform mixed oxides. The flowchart diagram of the sol-gel method as shown in
figure 3.9.

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 Figure 3. 9 Sol-Gel Method

3.4 Co-precipitation Method:

Utilizing a base within a solvent to precipitate metal in various forms of hydroxide using a
specific salt source was a part of the precipitation method. Chemical co-precipitation was a
straightforward and affordable technique for creating nanomaterials. Sulfides of metals produced
through co-precipitation do not require further heating. The flowchart diagram of the Co-
precipitation method as shown in figure 3.10.

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 Figure 3. 10 Co-precipitation Method

3.5 Solid State Method:

The solid-state chemical reaction method was a process that utilized for synthesizing phosphor
materials at extreme temperatures. One of the most common methods for creating solids with a
crystalline structure was a solid-state reaction approach.

 The particles are attracted to one another quite strongly.

 The distance between solid particles was quite small.
 It shows large density of the solids.
 Solids barely undergo compression.
The flowchart diagram of solid state method as shows in figure 3.10.

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Figure 3. 1 Solid State Structure

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 4 Result and Discussion
4.1 Preparation of PbAl2O4

The sol-gel method was utilized for synthesizing PbAl 2O4. Initially, 0.05 M of Pb(NO3)2 was
combined with 100 ml of distilled water while continuously swirling for seven minutes. To
achieve a homogeneous mixture, 0.1 M solution of Al(NO 3)2 was fabricated in 100 ml distilled
water as well as stirred at 10 minutes. Subsequently, the fabricated Pb(NO 3)2 solution was slowly
added to the 0.1 M solution of Al(NO 3)2 and stirred for 20 minutes before introducing 1.6 g of
acetic acid to the precursor solution, which acted as both a chelating agent and a binding agent.
Additionally, 5 mL of the ethylene glycol was incorporated into the reaction mixture to act as a
stabilizer and improve the final shape.

To maintain a pH level of 7-8, ammonia solution was included drop by drop, and the mixture of
reaction was heated to 80°C until gel formation occurred. After gel formation the mixture was
heated at 370 C and further dried in muffled furnace at 600˚c in a crucible. The final product was
grinded and send for characterizations.

4.2 Electrochemical Techniques:

The electrochemical study performance was completed by the help of:

 CV
 EIS
 GCD
 Chronoamperometry

4.2.1 Cyclic Voltammetry:

Figure 4.1 shows the cyclic voltammetry (CV) curves of PbAl 2O4 electrode material with the
potential range between (-0.1 to 0.6 V) generated for different scan rates ranging from 5 to 50
mV s-1. When the scan rates increasing, both current and the area of CV curve also growing, but

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the Cs decreases because as well as growing scan rate, then ions in electrolyte travel faster,
thereby decreasing their ability to interact as well as entire active area of a working electrode. At
decreasing scan rates, ions have more time for appropriate interaction, resulting in an increased
specific capacitance as shown in figure 4.2. The spinel high-entropy oxide prepared in this work
contains two post-transition metals capable of conducting redox reactions: Pb and Al.
Furthermore, these metals may have varying oxidation states that favor faradaic reaction.

The cyclic voltammetry curves exhibit the 0.4V of the oxidation peak, attributable to oxidation
of transition metal oxides. Simultaneously, reduction peak was centered at 0.25V, which may be
ascribed to the decreasing of pos-transition metal oxides. Consequently, energy storage occurs
through rapid and cyclic redox reactions at electrode's surface, indicating that charge storage
system was pseudocapacitiv. The specific capacitance (Cs) was calculated of following equation

Cs = A / (2mkv)

Here A is the area, m represents the mass, and k indicates scan rate as well as v represents the
applied potential.

The assessment of cyclic voltammetry curves derived from pure nickel foam as well as
PbAl2O4/nickel foam at a scan rate of the 50 mV/s, clearly demonstrating the difference. The
central part of CV curve generated from clear NF was extremely small, indicating that the
capacitance provided by the NF can be disregarded.

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Figure 4. 1 Cyclic Voltammetry

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 Figure 4. 2 Specific Capacitance vs. Scan Rate

4.2.2 Electrochemical Impedance Spectroscopy:

Electrochemical impedance spectroscopy was a method to solve the electrical characteristics
associated with the electrode-electrolyte system. The EIS profiles of the high-entropy oxide
electrode were captured as a cycling stability assessment at the spread out circuit potential,
utilizing the AC signal along with a 5mV amplitude as well as a frequency range spanning
between 0.01Hz to 100 kHz. The EIS information was adjusted using the parallel circuit that

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includes a solution resistance (Rs), a constant stage element (Q), a charge transfer element (Rct),
and a pseudocapacitive component (C), as represented in Fig. 4.4. The analysis indicates that the
Rs for the high-entropy oxide electrode measures 0.874mΩ, while the Rct measures 1.07 Ω. The
low resistance indicates that more ions move to deposit on the material, thereby exciting the most
electrons from the material, resulting in an increase in specific capacitance.

Figure 4. 3 Electrochemical Impedance Spectroscopy by Fit

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4.2.3 Galvanostatic Charge Discharge:

The galvanostatic charge/discharge (GCD) curves of the PbAl 2O4 electrode material also exhibit
pseudo-capacitive properties, as depicted in Fig. 4.4. These curves were calm in a potential
window between (-0.1 to 0.6 V), across distict current densities ranging between 1 A/g to 5 A/g.
The Cs of PbAl2O4 was 852.48 F/g, 706.64 F/g, and 649.99 F/g were found for current densities
1 A/g, 3 A/g, and 5 A/g, correspondingly. The higher current densities cause the material to
charge and discharge at a faster rate, which can limit ion diffusion and charge transfer inside the
material. These constraints can result in a decrease in the material's effective capacitance at
greater current densities compared to lower ones. The electrode material exhibits a rate capacity
of 38% from 1 A/g to 5 A/g. additionally, the capacitance was calculated using following
Equation integrating of the area of the discharge curve for the non-linear charge and discharge
curve. When the current density of 1 A/g, the Cs measured 852.48 F/g also maintained a Cs of
649.99 F/g at an extremely high current density of 5 A/g. Because at higher current densities the
release time decreases that’s why the obtained Cs is lower at higher current densities as shown in
figure 4.5. Cs was estimated using the GCD curve in the potential window suspend the IR drop,
where internal resistance (IR), V is the ohmic drop during the constant current's polarization
reversal.

Cs = (I × dt) / (m × dv)

Where Cs represents of specific capacitance, m is the loaded mass, I is the current, dt is the
change of time and dv indicate the change potential.

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Figure 4. 4 Galvanostatic Charge Discharge

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Figure 4. 5 Specific Capacitance vs Scan Rate

Page 44
Figure 4. 6 Power Density vs Energy Density

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 Comparison Table 2

Sr. Material Name Electrode Electrolyte Specific Scan Rate Reference

No Name Capacitance (A g-1)
(F g-1)
1 (CoCrFeMnNi)3O4 Nickel 2 M KOH 239 0.5 [43]
Foam
2 NiO-MnO2 Nickel 1 M KOH 1027 1 [44]
Foam
3 NiCo2O4 Stainless 6 M KOH 1411 1 [45]
Steel
Substrate
4 FeCo2O4 Nickel 2 M KOH 853 5 [46]
Foam
5 ZnFe2O4 Carbon 1M H2SO4 1598 1 [47]
Cloth (CC)
Substrate
6 ZnSm2O4 Nickel 1 M KOH 1908 0.03 [48]
Foam
7 MnNiCo Nickel 6 M KOH 483 0.5 [34]
Foam
8 MnCo2S4 Nickel 3 M KOH 1402 1 [49]
Foam
9 NiCoFe2O4 Nickel 1 M KOH 638 1 [50]
Foam

4.2.4 Chronoamperometry:
The capacitance retention remains at 95% at 2000 cycles, exhibiting exceptional cycling
stability. Chronoamperometry was used to confirm the electrode stability. As demonstrated in
Fig.4.7, the curve remained straight for 33 hours at a voltage of 0.76 V when related to the
reference electrode. The Nanosheet’s mesoporous surface characteristics of the electrode can
achieve remarkable electrochemical performance. These characteristics provide a vast surface
area and numerous electroactive locate for redox reactions. Moreover, the free space between the
nanoparticles may function as an ion sink, allowing for greater electrolyte penetration into the
electrode's surface.

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 Figure 4. 7 Chronoamperometry

Conclusion:
The sol-gel method was utilized to fabricate the high entropy oxide PbAl 2O4 materials for
supercapacitor applications. The PbAl2O4 materials shows a good specific surface area, high
capacitance, and good conductivity during electrochemical investigation. The PbAl 2O4 materials
were electrochemically tested for supercapacitor applications and the prepared materials were
deposited on NF and it was acting as a usable electrode, utilizing 3 M KOH electrolyte. At Cd 1
A/g, the electrode materials have high Cs of 852.48 F/g. Even after 1000 cycles, the material
maintained the capacitance retention of 76%. This study was best examine to first utilization of
pristine spinel-type nanoparticles for supercapacitor applications.

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