FACILE SYNTHESIS OF NANO-STRUCTURED Ni(OH)2-MnO2-rGO

COMPOSITE VIA GELATION METHOD FOR POTENTIAL

SUPERCAPACITOR ELECTRODE MATERIAL

By

MD. YEASIN ARAFAT TAREK

In the partial fulfillment of the requirement for the degree

of
MASTER OF SCIENCE IN CHEMISTRY

Department of Chemistry
BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY
(BUET),
DHAKA-1000
June 2021
 CANDIDATE’S DECLARATION

It is hereby declared that this thesis or any part of it has not been submitted elsewhere for the
award of any degree or diploma.

Md. Yeasin Arafat Tarek

 DEDICATION
I dedicate this thesis to my beloved junior late Kazi Rifat Mamun (1995-2019).
Kazi Rifat Mamun was an M.Sc student of the Department of Chemistry,
BUET (April-2019) session. In early 2019, Rifat died of Guillain-Barré
syndrome (GBS).
He had completed his B.Sc degree in Chemistry from Khulna University in
2019. Rifat was a talented young star and dedicated person who involved
himself in fundamental research. He was a very brilliant, polite, innocent
person I have ever seen. May Allah grant his soul and award him Jannah.
He came along with Ragib, Rumon (batchmates) to get himself enrolled in the M.Sc program.
They were passing their life with tremendous joy and happiness. It is suspected that Rifat got ill
after consuming contaminated water or food. But, in reality, the exact reason for GBS is yet
unknown.

My dear Rifat,
Tell me there's a river I can swim that will bring you back to me
'Cause I don't know how to love someone else
I don't know how to forget your face. Oh, love!
God, I miss you every single day when you're so far away
Rest in Peace.
 Table of Contents
Page No.
Graphical Abstract 01

Abstract 01

CHAPTER 1

1. Introduction 02

1.1 Energy Storage Device 02

1.2 Problem regarding present supercapacitors and its solution 09

References 14

CHAPTER 2

2. Experimental Section 18

2.1 Materials and Chemicals 18

2.2 Synthesis of MnO2 by the gel formation method 18

2.3 Synthesis of NiO-MnO2 19

2.4 Synthesis of rGO 20

2.5 Synthesis of NiO-MnO2-rGO (Ex-situ preparation method) 20

2.6 Synthesis of Ni(OH)2-MnO2-rGO (In-situ preparation method) 21

2.7 Cell setup, fabrication of electrode and electrochemical measurements 21

2.8 Characterization 22

References 22
CHAPTER 3

3. Results and Discussion 23

3.1 Synthesis of Materials 23

3.2 Electrochemical and Capacitive Performance 26

3.2.1 Cyclic Voltammetry and Galvanostatic Charging-Discharging 26

3.2.2 Impedance Analysis 33

3.2.3 Cyclic Stability 34

3.2.4 Active Mass Variation and GO Weight Optimization 35

3.3 Structure, Morphology and Elemental analysis 37

3.3.1 Structure and Surface Morphology Analysis 37

3.3.2 Elemental Analysis 41

3.3.3 Functional Group Analysis 42

References 44

CHAPTER 4

4. Conclusion 50

4.1 Conclusion 50

4.2 Future Aspects of this Research 50

Figures

Figure No. Figure Caption Page No.

Transformation of electrical energy in several sectors of modern
Figure 1.1 02
society (21st century)
Figure 1.2 Conventional (a) Lithium-ion (b) Nickel-cadmium (c) Lead-acid
03
and (d) Nickel metal hydrate batteries
(a) Electrochemical behavior of several types of batteries. (b)
Figure 1.3 04
Conceptualization of energy and power density
Figure 1.4 Comparison between conventional capacitor and supercapacitor 06
(a) Comparison of energy and power density of energy storage
Figure 1.5 07
devices, and (b) Cyclic stability of storage devices
Charge storing mechanism of (a) EDLC (b) Hybrid and (c)
Figure 1.6 08
Pesudocapacitor supercapacitor
Schematic illustration of the growth of Ni(OH)2-MnO2 on rGO
Figure 1.7 12
surface
Schematic presentation of MnO2 preparation by gel formation
Figure 2.1 18
method
Schematic diagram of formation of NiO-MnO2 via simple gel
Figure 2.2 19
formation method
Synthesis scheme of GO and subsequent chemical reduction of
Figure 2.3 20
GO to produce rGO
Symmetrical assemblies of two-electrode setup and
Figure 2.4 21
electrochemical data acquisition
Illustration of the cross-linking proposed for (Mn2+.Mn3+) oxides
Figure 3.1 23
gels
(a) CV and GCD of neat MnO2 and (b) CV and GCD of NiO-
Figure 3.2 27
MnO2
Figure 3.3 CV and GCD of rGO synthesized by modified Hummers method. 28
(a) CV and GCD of NiO-MnO2-rGO (ex-situ synthesis process)
Figure 3.4 and (b) CV and GCD of Ni(OH)2-MnO2-rGO in situ synthesis 29
process
(a) Comparison of Cyclic voltammetry curve of (MnO2, NiO-
MnO2, NiO-MnO2-rGO, rGO, and Ni(OH)2-MnO2-rGO). (b)
Figure 3.5 Comparison of Galvanostatic charging and discharging curve of 31
(MnO2, NiO-MnO2, NiO-MnO2-rGO, rGO, and Ni(OH)2-MnO2-
rGO)
(a) Ragone plot for comparing the supercapacitor performance of
Figure 3.6 synthesized materials. (b) Variation of specific capacitance with 31
various current densities
Figure 3.7 EIS of (MnO2, NiO-MnO2, NiO-MnO2-rGO, rGO, and Ni(OH)2-
33
MnO2-rGO)
Cyclic stability test of Ni(OH)2-MnO2-rGO composite at a current
Figure 3.8 35
density of 10 Ag-1
 (a) Variation of specific capacitance with different mass loading
Figure 3.9 and (b) variation of specific capacitance with the variation of the 36
amount of GO required during the preparation
XRD patterns of MnXOY, NiO-MnXOY, and Ni(OH)-MnO2-rGO
Figure 3.10 38
composite
(a) SEM image of capsule shaped MnXOY (b) SEM image of rod
Figure 3.11 shaped NiO in MnXOY and (c,d,e,f) SEM images of Ni(OH)2- 40
MnO2-rGO
Red circles denote the presence of Ni(OH)2 and green circles
Figure 3.12 41
denote the MnO2
Figure 3.13 EDX spectra of Ni(OH)2-MnO2-rGO 42
Figure 3.14 FT-IR spectra of Ni(OH)2-MnO2-rGO, MnXOY and NiO-MnXOY 42

Tables
Table No. Table Caption Page No.
Summarized electrochemical performance of (MnO2, NiO-MnO2,
Table 1 NiO-MnO2-rGO, rGO, and Ni(OH)2-MnO2-rGO). 32

Summary of the Rs and Rct values for the synthesized

Table 2 34
nanomaterials.

List of Abbreviations of Technical Symbols and Terms

1. GO – Graphene Oxide
2. rGO – Reduced graphene oxide
3. Csp – Specific capacitance
4. E – Energy density
5. P – Power density
6. i/m – Current density
7. ΔV – Potential difference
8. Δt – Discharging time
 Acknowledgement

At the very beginning, I humbly acknowledge my deepest gratitude to the almighty, the most
gracious, benevolent and merciful creator for his infinite mercy bestowed on me in carrying out
the research work presented in the dissertation. It is a great pleasure for me to acknowledge my
deepest sense of gratitude, sincere, appreciation, heartfelt indebtedness, and solemn regards to my
reverend teacher and supervisor Dr. Md. Shakhawat Hossain Firoz, Professor, Department of
Chemistry, Bangladesh University of Engineering and Technology (BUET), for his kind
supervision, indispensable guidance, valuable and constructive suggestions, liberal help, and
continuous encouragement during the whole period. His attributive contribution and efforts have
greatly shaped me into what I am today. I am quite fortunate to be a part of his ambitious research
team. I would like to convey my deepest gratitude to Dr. Al Nakib Chowdhury, and Dr. Chanchal
Kumar Roy for their valuable suggestions appreciated comments, guidance, and help during the
research period. I am thankful to all other respected teachers of the Department of Chemistry,
BUET, for their time to time support. I would also like to thank all of the officers and staff of the
Department of Chemistry, BUET for their continuous help during my study period. I am highly
grateful to all members of the board of examiners for their valuable suggestions and appreciated
comments. I am thankful to my dear colleagues and all the members of my Research Group for
their friendly cooperation and lovely encouragement throughout my research period. Special
thanks to Md. Ragib Shakil, Hridoy Roy Prottoy, Md. Akter Hossain Reaz, Md. Mahmudul Hasan
Rumon, Sanjida Afrin, and Maherun Negar Majumdar for their continuous help during the
research.

I am also thankful to other fellows of the Materials Chemistry Laboratory for their cooperation
during the research period. I am grateful to the authority of BUET and the ministry of Science and
Technology for their financial support in this research. Finally, I would like to express my heartfelt
indebtedness and profound gratitude to my beloved father, mother, and all of my family members
for their continuous inspiration and immeasurable sacrifices throughout my study.

June 2021 Md. Yeasin Arafat Tarek

ABSTRACT

GRAPHICAL ABSTRACT

ABSTRACT
This research work represents the facile synthesis of self-assembled hybrid Ni(OH)2-MnO2-rGO
composite by a simple gel formation technique. The electrochemical study was conducted to
evaluate the supercapacitor performance of the as-prepared Ni(OH)2-MnO2-rGO electrode
material using 0.5 M Na2SO4. Due to the abundant self-assembled layered nanostructure of rGO
and hydrothermally grown Ni(OH)2 as well as MnO2 on rGO surface, the composite exerts
relatively high surface area and well-defined spherical morphology. The synergetic effect of
Ni(OH)2, MnO2, and rGO in Ni(OH)2-MnO2- rGO ternary hybrid as active materials exhibited
significantly enhanced specific capacitance (320 Fg-1) and energy density (11.11 Whkg-1) at
1 Ag-1 current density, based on the total mass of active materials. In addition, the Ni(OH)2-MnO2-
rGO hybrid structure-based symmetric supercapacitor also showed satisfying power density (250
Wkg-1) and electrochemical cycling stability (2000 cycles). The solution resistance (Rs) for the
Ni(OH)2-MnO2-rGO was found 4.7 Ω and after 2000 cycles the capacitance retention was 92 %
of the initial value. As a result of those outstanding features, the hybrid composite of Ni(OH)2-
MnO2-rGO is considered as a highly prospective electrode material for supercapacitor
applications.

KEYWORDS: Hybrid Supercapacitor, Gel formation, Ni(OH)2-MnO2-rGO, Self-assembled,

ternary hybrid.

1
CHAPTER 1

CHAPTER 1
INTRODUCTION
1.1 Energy Storage Device
Electrical energy is the smartest and safest form of energy ever discovered by human beings. But,
still, in many developing and developed countries around the globe, electricity is producing by
burning diesel, natural gas, and coal [1,2]. This biofuel consumption is severely impacting the
global environment and threatening the healthy living assurance of human beings. As a
consequence of that many efforts and technologies have been developed to produce clean and safe
electrical energy, such as – nuclear fission reactor, windmill, hydroelectricity, etc. as the best
alternatives of fossil fuel consumption [3,4,5]. Besides, the solar energy conversion to electrical
energy added significant advancement in the energy harvesting sector. In the 21st century, the
demand for electrical energy with the transformation rate of society has reached its zenith level.
Now, electrical energy is not only limited to households or industrial applications but also
transforming into portable heavy or light devices including vehicles. Rather, the incoming
centuries will be solely dependent on the use of electrical energy just to overcome extensive global
emission and warming problems raised by the burning of fossil fuels.

Figure 1.1 Transformation of electrical energy in several sectors of modern society (21st century).

2
CHAPTER 1

However, producing the cleanest and safest electrical energy is not only a challenge to be solved
in the modern era. Rather, storing the produced electricity and utilizing it efficiently for the
required purposes is also considered a prime challenge. To serve this purpose, batteries are first
introduced in the mid of 18th century. Since then, the advancement in electrical energy storage
devices are continuously booming and in the 21st century, the advancements in Lithium-ion
batteries have reached their zenith level [6]. Today’s many portable electronics are run by mainly
Lithium-ion batteries and other conventional energy storage devices such as Nickel-Cadmium
batteries, Nickel Metal Hydride batteries, Lead-acid batteries, etc. (shown in Figure 1.2).

(c) Lead-acid battery

(b) Nickel -
(d) Nickel metal cadmium
hydrate battery
battery
(a) Lithium-ion
battery

Figure 1.2 Conventional (a) Lithium-ion (b) Nickel-cadmium (c) Lead-acid and (d) Nickel metal hydrate
batteries.

Besides battery devices, another type of electrical energy storage device is the capacitors. The
basic mechanism of these batteries and capacitors are very similar [7]. It is important to understand
the basic differences between capacitors and rechargeable (secondary) batteries in the way they
function. Generally, a battery consists of a positive electrode (cathode), a negative electrode
(anode), and an electrolyte that allows ions to move from anode to cathode during discharge and
return during recharge [8]. The voltage developed across the battery terminals varies according to
the type of battery and the chemistry involved between the electrodes and electrolytes. In Figure

3
CHAPTER 1

1.3 (a), electrochemical reactions typical of rechargeable batteries and their operating voltages are
shown. The fundamental difference between batteries and capacitors is that the former store's
energy in the bulk of chemical reactants capable of generating charge, whereas the latter store's
energy directly as surface charge. Battery discharge rates and therefore power performance is then
limited by the reaction kinetics as well as the mass transport, while such limitations do not apply
to capacitors, thereby allowing exceptionally high power capability during both discharge and
charge [9].

Figure 1.3 (a) Electrochemical behavior of several types of batteries. (b) Conceptualization of energy and
power density.
Hence, the batteries possess high energy density with limited power density but capacitors have
high power density with limited energy density. Energy and power are often used to describe the

4
CHAPTER 1

characteristics of any energy storage device. Power density is simply defined as the amount of
electrical charge released at a time from a device, and energy density is the storage capacity of
charges in the devices [10]. As an example, If the energy storage device is used in an electric
vehicle, power density shows how fast one can go, and the energy density shows how far one can
go on a single charge. Capacitors put out enormous power, but store only tiny amounts of energy,
similar to the behavior of the water cup in Figure 1.3 (b). On the contrary, batteries store a fair
amount of charge but charge and discharge slowly, similar to the large water bottle in Figure 1.3
(b). Although the energy density of batteries is high enough, the power density is not optimum for
supporting heavy equipment like- electric cars, electric trains as well grid-level storage systems.
To ensure the utilization of electricity in electric vehicles or grid-level storage, a new class of
energy storage devices with optimum power and energy density is required to meet the challenges
of electrical transformation.
Supercapacitor or ultra-capacitor is an innovative technology that fills the gap between batteries
and capacitors. These energy storage devices behold significant characteristics which make them
efficient and capable to combine the energy storage properties of batteries and the power discharge
properties of conventional capacitors [11]. So, there are three classes of capacitors such as-
electrostatic, electrolytic, and electrochemical or supercapacitors [12]. In electrostatic capacitors,
the electrical charge stored through physical reactions, and hence they provide the lowest energy
density compared to the other two classes. Electrolytic capacitors work by growing insolation on
a rough metal surface like etched aluminum and this type of capacitor has 10 times higher energy
density than electrostatic capacitors [13].

But, the electrochemical capacitors process electric double layer capacitance (EDLC) at the solid
electrolyte interface and that ensures impressive capacitance (10000 times greater than electrolytic
capacitors) [14]. The capacitor stores charge electrostatically in an electric field and the amount of
charge is measured by its capacitance, C, which is a function of the area of the metal plates, A, and
the spacing between them, d. For typical capacitors, d ≈ 1 µm and A < 1 m2 (see Figure 1.4). So,
to increase the amount of charge stored, one needs to minimize d and maximize A and that is what
a supercapacitor does. A supercapacitor consists of two electrodes separated by an ion-permeable
separator to prevent short circuits between the electrodes and the cell is impregnated with a liquid
electrolyte [14]. As the potential is applied to a supercapacitor, ions from the electrolyte diffuse
into the pores of the electrode of opposite charge. Charge accumulates at the interface between the

5
CHAPTER 1

electrodes and the electrolyte, forming two charged layers (known as electric double layers) with
an extremely small separation distance on the order of 1 nm. The current supercapacitor technology
uses activated carbon as the active electrode material since this material is electrically conductive
and exhibits an extremely large surface area on the order of 1000-2000 m2/g, meaning that high
capacitance values can be achieved in a small space. For instance, comparing a capacitor and a
supercapacitor of similar volume shown in Figure: 1.4, the capacitor stores only 0.003 F, whereas
the supercapacitor stores >10,000 times more charge – about 50 F.

Figure 1.4 Comparison between conventional capacitor and supercapacitor.

Supercapacitors have several advantages over conventional energy storage devices which makes
it feasible to be implemented in the next generation vehicles:

I. Supercapacitors perform mid-way between conventional capacitors and batteries. They

offer higher energy density than conventional capacitors and higher power density than
batteries,
II. Supercapacitors can be charged in seconds, compared to hours for batteries and
milliseconds for capacitors.

6
CHAPTER 1

III. Supercapacitors store charge in a highly reversible process. Typical rechargeable batteries
last only for a few hundreds of charge/discharge cycles, whereas supercapacitors can be
used up to a million cycles.
IV. Environmentally friendly—no heavy metals or disposal issues as is common for
conventional batteries.
V. Supercapacitors can be operated under extreme working conditions. For example,
supercapacitors can be used at temperatures as low as −40 °C, where batteries cannot
function properly.
VI. Maintenance-free—providing superior cost-over-life, and fit-and-forget.

Figure: 1.5 (a) Comparison of energy and power density of energy storage devices, and (b) Cyclic stability
of storage devices.

Based upon the storage mechanism, electrochemical capacitors can be categorized broadly into
two groups namely double-layer capacitors and pseudocapacitors. In EDLC, electrical energy
storage occurs at the phase boundary between an electrode (electronic conductor) and the
electrolyte solution (liquid ionic conductor) with no involvement of charge transfer [15].
Moreover, the current generated in this type of capacitor is merely a displacement current due to
charge rearrangement or better known as an ideally polarized electrode.

7
CHAPTER 1

Figure: 1.6 Charge storing mechanism of (a) EDLC (b) Hybrid and (c) Pesudocapacitor supercapacitor.

The layer formation on the electrodes is called the Helmholtz layer. On the opposite, fast faradaic
redox reactions caused by redox-active species involving metal oxides and conducting polymers
with electrolytes are responsible for the potential determining charge transfer reaction that induces
the charge storage mechanism of pseudocapacitors [16]. The capacitance and power density of
pseudocapacitors are satisfactory compared to EDLC based materials, but the cyclic stability of
pseudocapacitors is so poor that alone pseudocapacitors cannot solve the commercial crucial
demand of cyclic stability. The destructive redox reactions are responsible for the unstable cyclic
stability because, during these reactions, the surface morphology changes its phases and blocks
accessible surfaces for incoming electrolytes. Towards this solution, merging these two types
(EDLC and pseudocapacitors), hybrid capacitors are introduced to the supercapacitors family. This
new hybrid type of capacitors can eventually be able to fulfill the energy and power density
demand at a time as it stores charges in both faradic and non-faradic ways.

So, supercapacitors have a wide range of applications not only in electronics but in automobiles
as well. These devices are designed with various capacitance values to cater to different industrial
requirements. Electronics applications such as cell phones and digital cameras, medical devices,
and uninterruptible power supplies depend on supercapacitors ranging from 1 F to 150 F.
Meanwhile, power backup in industrial and Telecom based station and renewable energy systems
require supercapacitors with the capacitance value ranging from 300 F to 350 F. Higher
capacitance supercapacitors (650 F to 3000 F) are designed for automotive subsystems, hybrid
drive trains, rail system power, heavy transportation and many other applications. Besides, this
technology has overcome the environmental issues whereby discarded batteries that may cause

8
CHAPTER 1

serious disposal waste are controllable. Moreover, the market interests in supercapacitors are
expected to grow due to their greater power and longer shelf life that may lead to a greener
environment.

1.2 Problem regarding present supercapacitors and their solution

The development of a supercapacitor includes the designing of the proper electrode materials with
a suitable combination of electrolytes. Designing electrode materials that can meet the present
power demands with suitable electrolytes and less hazardous have become a global concern.
Presently, researchers are not only focusing on developing high-performing, cost-effective
materials but also on sustainable technologies. However, the crucial importance is to maintain the
power capability, fulfilling the cycle life requirements as well as increasing the capacitance and
energy density performance. Usually, the pseudocapacitive materials are self-destructive in nature
due to their redox properties. Owing to their poor dissolution and less conductivity issues, pure
metal oxides or mixed metal oxides are not suitable enough for being an ideal commercial
electrode material. Commercial electrodes demand thousands of cycle life with a high discharge
rate to meet the industrial challenges. So, various ways have been developed to achieve these
criteria such as mixing the metal oxides to become binary or ternary oxides, compositing the metal
oxides with carbonaceous materials like activated carbons, fibers, aerogels, xerogels, fullerenes,
or nanostructures of graphene, as well as the incorporation of the metal oxides with conducting
polymers. The hybrid materials are expected to resolve the power and cyclic stability issues at the
same time.

Adopting nanotechnology in optimizing the microstructure of the electroactive materials in the

electrodes has become a notable issue as the charge storage system in pseudocapacitors involves
the first few nanometers from the surface [17,18]. So, the first requirement for an ideal high-
performing electrode is increasing the accessible large surface area with highly oriented
nanostructures. Moreover, active material with a smaller particle size may contribute to higher
capacitive performance due to the larger contact area between the electrode/electrolyte in
nanostructured oxides. This architecting ensures greater power delivery and better cycling stability
during the electrochemical performance which is highly desirable for the commercial fabrication
of supercapacitors [19]. Undoubtedly, nano dimensional materials possess high electrical
conductivity than bulk materials which makes them promising energy storage candidates in the

9
CHAPTER 1

current situation [20]. But, there is no hard and fast rule for optimizing proper electrode materials
in nano dimensions. Therefore, much research effort has been poured into developing effective
methods in the preparation of nanostructured metal oxides, metal hydroxides, and their composite
with carbon-based materials in various forms like nanoparticles, nanofibers, nanorods, nanowires,
nanotubes, nanosheets, and so on. Approaches that have been attempted by researchers to
synthesize nano dimensional metal oxides and nanostructured carbon-based electrode materials
are precipitation [21,22], solvothermal [23], hydrothermal [24,25], sol-gel [26], room-temperature
solid-reaction route [27], chemical bath deposition [28], anodization [29], electrochemical
deposition [30,31], lithographically patterned nanowire electrodeposition (LPNE) [32],
electrospinning [33] and others.

Besides electrode materials, the proper selection of electrolytes is also crucial. The capability of
organic electrolytes to withstand large potential window are overshadowed by their volatile, highly
flammable and toxic properties. Although aqueous electrolytes have the disadvantage of water
decomposition, they are relatively less harmful to the environment. However, concentrated acids
and bases can be corrosive and deleterious as well. Thus, the use of neutral electrolytes like Na2SO4
will be a desirable way in the development of supercapacitors with the hope of optimizing the
electrochemical performance while conserving nature.

The transition metal oxides (TMOs) with accessible variable oxidation states are prominent
candidates for pseudocapacitor materials [34,35]. From this perspective, different TMOs for
example, Ruthenium oxide (RuO2) have been extensively studied for their high capacitance
performance [36]. However, natural unavailability, high cost, complexities in preparation
techniques, and toxicity have limited the commercial energy storage applications of the material.
Manganese oxide-based pseudo-capacitive materials are a better alternative to other TMOs due to
their low cost, abundance, and environmental friendliness [37]. However, there is a great
difference between the theoretical (1370 Fg-1) and the measured specific capacitance of manganese
oxide-based materials [38]. The electrochemical dissolution and poor electrical conductivity are
the major drawbacks of manganese-based materials. So, the key trick to developing high-
performance hybrid supercapacitor materials is to improve the accessibility of electrolytes and
transportation of electrons by the proper nano-architecting of structure and morphology. However,
it can be resolved by the use of mixed or binary transition metal oxide composites formed with

10
CHAPTER 1

carbonaceous materials like reduced graphene oxide (rGO), which might increase the charge
transfer rate in addition to the fast-reversible redox reaction [39]. The synergistic effect of mixed
metal oxides or hydroxides with rGO is expected to facilitate the movement of electrical charge
within the electrode and hence improving the performance significantly. The enhanced and shaped
surface area of rGO plays a tremendous role in increasing the capacitance with mixed metal oxides
or hydroxides. Because the incorporation always facilitates the expanded rGO layers to
insert/disinsert the electrolytes ion in the electrodes. Usually, the fabrication of multiple oxides or
hydroxides of transitional metal within rGO layers is very challenging due to the high
agglomeration nature of rGO sheets. Besides, the electrical conductivity, as well as well-defined
morphology in the metal oxides or hydroxides, is entirely dependent upon the synthesis technique.
In that case, manganese oxides can be modified with other metal oxides or hydroxides of Ni, Co,
etc.

For the preparation of mixed metal oxide nanoparticles of manganese, NiO will be a very suitable
choice because of its high theoretical specific capacitance (2584 Fg-1) [40]. NiO has been
extensively studied for supercapacitive performance. Depending on the type of preparation
methods, many efforts have been made to synthesize MnO2 based mixed and ternary composite
for the application in supercapacitors which was reported earlier [41-44]. Junjiao Chen et. al
fabricated NiO@MnO2 core/shell nanocomposites by a two-step method that exhibited a specific
capacitance of 266.7 Fg-1 at 0.5 Ag-1 [45]. Bingjie Zhang et. al synthesized NiO-MnO2 core/shell
nanocomposite via a single-step hydrothermal method which also showed a high specific
capacitance of 528.0 Fg-1 at a scan rate of 1 mVs-1 [46]. Yuhong et. al reported a microwave-
assisted solid-state synthesis procedure of NiO-MnO2 composite, and that exhibits high specific
capacitance [47]. Among different synthesis methods for metal oxide, the sol-gel method or
modified gel formation method has demonstrated superiority for the formation of uniform particles
and control over the synthesis process [48].

In this study, a facile synthesis route of manganese oxide will be proposed which includes a one-
step gel formation method. The precursor will be calcined to get pure manganese oxide.
Subsequently, NiO will be doped in the manganese oxide nanoparticles by following the same gel
formation method to get the binary oxide. However, rGO incorporation into the mixed oxides will
be done in two different ways, i.e.; ex-situ and in situ incorporation. The ex-situ incorporation of

11
CHAPTER 1

NiO-MnO2 into rGO is always difficult and inefficient due to the structural integrity of the rGO
layers. But, in-situ incorporation is always efficient because it works with the growth formation of
oxides and hydroxides on the rGO surface.

Figure: 1.7 Schematic illustration of the growth of Ni(OH)2-MnO2 on rGO surface.

In ex-situ preparation, the readily prepared NiO-MnO2 will be mixed with rGO solution and that
will have resulted in NiO-MnO2-rGO formation. But, in-situ involves the mixing of rGO with
starting materials in the gel formation step and subsequently to the hydrothermal growth. As a
result, Ni(OH)2-MnO2-rGO formation occurs during the in-situ process.

Gel formation methods are less expensive over traditional sol-gel method because it avoids the use
of expensive alkoxides. However, most of the synthesis process earlier reported for the synthesis
of pure manganese oxides and hybrid nickel-manganese oxides followed multiple steps. The
processes are time-consuming and expensive as well as not environment friendly. Herein, we have
reported a facile one-step gel formation method to prepare Ni(OH)2-MnO2-rGO mixed oxide
nanoparticles using glycerol, an environmentally benign reducing agent. The synthesized

12
CHAPTER 1

nanomaterials have a hierarchical nano-architectured structure with excellent supercapacitive

performance which is promising for the applications of supercapacitor material.

Objectives:
The main objectives of this work are to
I. prepare MnO2 and NiO-MnO2 nanoparticles by a simple gel formation method and
examine the electrochemical capacitive performances by cyclic voltammetry (CV),
galvanometric charging-discharging (GCD), electrochemical impedance (EI), and
cyclic stability.
II. fabricate Ni(OH)2 -MnO2 -rGO nanocomposite with the incorporation of Ni(OH)2 and
MnO2 in the rGO nanosheets by in-situ reaction and examine the electrochemical
performances by CV, GCD, EI, and cyclic stability.
III. rationalize the specific capacitance and cyclic stability of MnO2, NiO-MnO2, Ni(OH)2
-MnO2-rGO, and NiO-MnO2-rGO nanocomposites.
IV. investigate the composition and morphology-dependent chemical and physical
properties of the synthesized nanocomposites by scanning electron microscopy (SEM),
X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FT-IR).

13
CHAPTER 1

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47. Bi, Y., Nautiyal, A., Zhang, H., Luo, J., & Zhang, X. (2018). One-pot microwave synthesis
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17
CHAPTER 2

CHAPTER 2
EXPERIMENTAL SECTION
2.1 Materials and Chemicals

In this study, analytical grade potassium permanganate (Merck, Germany), Nickel chloride
(Merck, Germany), Glycerol (JHD, China), Sodium hydroxide (Merck, India), Sodium thiosulfate
(Merck, Germany), Polyvinylidene fluoride (Merck, Germany), Dimethyl sulfoxide (Lab-Scan,
Ireland), Hydrogen peroxide (Merck, Germany), Hydrochloric acid (Merck Germany), Hydrazine
hydrate (Merck Germany), Graphite powder (Merck Germany), and Ethanol (Merck, Germany)
were purchased and used without further purification. Aqueous solutions of all the experiments
were prepared using deionized (DI) water (18.2 MΩ-cm of resistivity at 25 OC).

2.2 Synthesis of MnO2 by the gel formation method

Manganese Oxide (MnO2) was synthesized by adopting a simple gel formation method. In a typical
reaction, 0.3M KMnO4 (100 mL) was firstly prepared in a beaker under vigorous sonication. After
that 0.3M (50 mL) Glycerol solution was prepared and poured dropwise from a burette in the
prepared KMnO4 solution under vigorous magnetic stirring. After mixing the whole glycerol
solution, a brown color gel was readily formed. The system was allowed to continue for the next
30 minutes. The gel was then left undisturbed for the next 24 hours.

Figure 2.1 Schematic presentation of MnO2 preparation by gel formation method.

18
CHAPTER 2

After 24 hours, the gel was found to be settled down in the beaker. The supernatant was removed
so that the gel could be completely dried at 80 °C in the hotplate. Then it was collected and ground
in a mortar pestle. The ground powder was washed with distilled water and centrifuged several
times to remove any residual K+ ions. After complete washing, the gel was washed with some
alcohol to remove any other impurities in the gel. However, the washed precursor was then dried
in a hot air oven at 80 °C to get a dried brownish color powder. A part of this sample was collected
in a vial for further testing and another part of the sample was calcined at 700 °C (10 °C /min, 6
hours) to complete oxide formation.

2.3 Synthesis of NiO-MnO2

NiO-MnO2 mixed oxide was prepared by incorporating Ni(OH)2 in the vicinity of the manganese
oxide preparation. In brief, 0.27M NiCl2.6H20 (50mL) was prepared by dissolving (3.47 g)
NiCl2.6H20 in deionized water. Then, 0.4 g of NaOH was dissolved in 50 mL water and added to
the nickel chloride solution to prepare a greenish suspension of Ni(OH)2. This readily prepared
Ni(OH)2 was incorporated dropwise by another burette in the previously mentioned 0.3 M KMnO4
solution simultaneously with 0.3 M glycerol using a similar method used in the preparation of
MnO2. A brownish gel formation took place instantly. The reaction was allowed to proceed for the
next 30 min.and then allowed to be settled down for the next 24 h. Excess potassium ion was
removed by repeated centrifugation and the product was set in the hot air oven at 80°C for complete
drying. The dried brownish powder was then collected and heat-treated in the muffle furnace 700
°C (10°C /min) for 6 h under air to get the black powder of NiO-MnO2.

Figure 2.2 Schematic diagram of formation of NiO-MnO2 via simple gel formation method.

19
CHAPTER 2

2.4 Synthesis of rGO

To synthesize rGO, the GO was firstly synthesized by following the modified hummer method
[1,2]. To start with 2 g graphite flakes were mixed into 50 mL concentrated sulfuric acid. Under
continuous stirring, the mixture was cooled by using an ice-water bath and the suspension was
obtained. 6 g amount of oxidizing agent potassium permanganate (KMnO4) was added moderately
into the suspension under a controlled temperature below 10 °C. The suspension was then stirred
at room temperature for 25 min followed by sonication in an ultrasonic bath for 8 minutes. 250
mL distilled water was added into the mixture with repetition of stirring-sonication process 10
times. After that 30 mL hydrogen peroxide (H2O2) was added to exfoliated graphite oxide achieved
by ultra-sonication of dispersed solution for 1 h. After centrifugation of solution at 4000 rpm, GO
was washed with 2M HCl (to remove excess metal ion) and distilled water several times until the
pH was ~7. The resulting GO precipitates were dried at room temperature for 24 h.

Figure 2.3 Synthesis scheme of GO and subsequent chemical reduction of GO to produce rGO.

To obtain rGO, the above suspension was again sonicated for 2 h. Hydrazine hydrate was added
dropwise to the exfoliated graphite oxide suspension at room temperature. The reduction was
performed at 100 °C for 1 h. The weight ratio for hydrazine hydrate and GO was maintained at 9:7
for this sample. Resultant black precipitates were filtered by cellulose filter paper and washed with
a 1M HCl solution and distilled water to obtain neutral pH. Finally, the filtrate was dried at room
temperature for 24 h to obtain rGO sheets.

2.5 Synthesis of NiO-MnO2-rGO (Ex-situ preparation method)

20 mL of 0.20 g of rGO solution was mixed with 50 mL 0.3 M glycerol under vigorous magnetic
stirring. Then the previously prepared nanomaterial (NiO-MnO2) was mixed (ex-situ) directly with
20
CHAPTER 2

the rGO-glycerol matrix solution. The total reaction was allowed to continue for the next 2 hours.
Then, it was washed thoroughly with deionized water. After several washes, the precursor was
dried in a hot air oven at 80 °C for 6 hours. The dried black powder was expected to be the NiO-
MnO2-rGO powder prepared in an ex-situ setup.

2.6 Synthesis of Ni(OH)2-MnO2-rGO (In-situ preparation method)

Ni(OH)2-MnO2-rGO nanocomposite was prepared by a simple one-step gel formation process.

Typically, a mixture of Ni(NO3)2·6H2O (0.5 mmol) - glycerol (4.0 g) was slowly added to (0.3
mmol) KMnO4 solution containing 2.0 g of a homogeneous aqueous suspension of GO (0.20 g,
1.44 wt %) under vigorous magnetic stirring. Then, extra H2O (3.0 g), and glycerol (8.0 g) were
added to the final vessel. The as-obtained suspension was transferred to a 100 mL Teflon
autoclave. The autoclave was then sealed and kept at 180 °C for 24 h to allow the growth of
Ni(OH)2-MnO2-rGO hybrid material. After that, the product will be washed and dried to obtain
Ni(OH)2-MnO2-rGO nanocomposite.

2.7 Cell setup, fabrication of electrode and electrochemical measurements

Figure 2.4 Symmetrical assemblies of two-electrode setup and electrochemical data acquisition.

The electrochemical properties of the as-obtained synthesized materials were investigated under a
two-electrode cell configuration at 25 °C in 0.5M Na2SO4. The electrode materials were firstly
taken (10 mg) in a glass vial with 250 µL of (N-Methyl-2-pyrrolidone) NMP solution as a solvent,

21
CHAPTER 2

and (Polyvinylidene fluoride) PVDF as a binder (as shown in Figure 2.4). Then the glass vial was
subjected to sonication for the next 30 minutes to get a slurry of active materials. About 20 µL
(2mgcm-2) of slurry was pasted on two polished disk-shaped graphite electrodes. Both the
electrodes were dried under a hot air oven at 60 °C for 3 hours to evaporate all the solvents. One
of the electrodes was then put into the split coin cell and a separator made of Whatman Filter Paper
(pore size, 11 µm) was placed right on this electrode material very gently. Few drops of freshly
prepared 0.5 M Na2SO4 were poured on the filter paper. When the filter paper seems completely
wet, another electrode is placed upside down to this wet filter paper. Finally, the cap of the split
coin cell was assembled properly to complete the cell setup.

2.8 Characterization

The morphologies were observed by scanning electron microscopy (FESEM, S-4800, Hitachi).
The crystalline structure was characterized by XRD patterns recorded in a Rigaku D/max-kA
diffractometer with Cu Kα radiation. Elemental analysis was performed in energy-dispersive X-
ray spectroscopy (EDX, TSL, AMETEK), and FT-IR (Agilent Cary 630) measurements were
employed to investigate the compositions of the samples.

References

1. Sharma, N., Sharma, V., Jain, Y., Kumari, M., Gupta, R., Sharma, S. K., & Sachdev, K.
(2017, December). Synthesis and characterization of graphene oxide (GO) and reduced
graphene oxide (rGO) for gas sensing application. In Macromolecular Symposia (Vol. 376,
No. 1, p. 1700006).

22
CHAPTER 3

CHAPTER 3

RESULTS AND DISCUSSION

3.1 Synthesis of materials

The synthesized nanomaterials are namely MnO2, NiO-MnO2, rGO, NiO-MnO2-rGO and
Ni(OH)2-MnO2-rGO. During the preparation of manganese oxide nanoparticle, an exothermic
redox reaction shown in equation (1) are expected to be taken place. The strong oxidizing agent
KMnO4 readily reacts with the mild reducing agent glycerol. However, the dropwise addition of
KMnO4 to glycerol solution resulted in a dark brown color gel. The reaction was very fast and
completed within 30 minutes and the total reaction process was conducted at ambient atmosphere.

14 KMnO4 (s)+4 C3H5(OH)3 (l) ⟶ 7 K2CO3 (s) +7 Mn2O3 (s) +5 CO2 (g) +16 H2O (l) (1)

Upon heating on the hotplate at 80 °C, the dark brown gel started to form a crosslinking network
which is proposed in Figure 3.1. The exact composition of the as-prepared gel network is
unpredictable but from the literature, it is already known that the gel formation should proceed
through the reduction of MnO4- [1]. The cross-linked network shows the coexistence of manganese
oxides site with some partially oxidized glycerol fragments. The observation suggesting the
condensation reaction of the gel resulted in to form of manganese oxide nanocrystallites.

Figure 3.1 Illustration of the cross-linking proposed for (Mn2+.Mn3+) oxides gels.

23
CHAPTER 3

On further approach, the calcination process was conducted at 700 °C (10 °C /min, 6 hours) to
convert the crystalline cross-linked network into pure manganese oxide. The temperature and
ramping were optimized to get controlled growth of crystalline manganese oxide in the ultimate
product. However, several studies have been reported in the literature and suggest that the phase
transformation is an uncontrollable issue during the calcination process. As a result, different kind
of morphology and phase (MnO2, Mn2O3, Mn3O4, and Mn5O8) appears in the final product [2-4].
As an example, Ullah et al. have reported the formation of different manganese oxides with
different phases at different temperatures [5]. They found the complete transformation of
manganese oxide (Mn2O3) at 700 °C with a ramping of 50 °C. In our case, the ramping was
controlled to 10 °C and hence it was expected to get coexistence of manganese oxides in the final
product. The exact morphological confirmation of the as-prepared nanoparticle was conducted by
XRD and discussed in section 3.3.

However, the incorporation of NiO in the manganese matrix was conducted by the incorporation
of Ni(OH)2 suspension as shown in the Figure 2.3 in experimental section. Here, the Ni(OH)2
suspension was poured into the KMnO4 with glycerol simultaneously. Except this step, everything
was maintained as same as the reaction mentioned in equation (1). So, after 24 hours, a clear top
layer of water and the precipitation of the brownish gel containing Ni(OH)2 was found and that
confirmed the successful incorporation of Ni(OH)2 in the brown gel. If the incorporation become
failed, then instead of the clear top layer of water, a greenish color would have been found. The
Ni(OH)2 is expected to be distributed homogeneously as the hydrated form in the matrix shown in
Figure 3.1. After the calcination process at 700 °C (10 °C), the complete conversion of Ni(OH)2
to NiO was found and that is confirmed and discussed in the Figure 3.10. Although, according to
the literature, it is reported the conversion of Ni(OH)2 to NiO might have happened after 200 °C
[6-8]. So, in our case, the conversion was expected to be a complete conversion as the temperature
was high during the calcination process of mixed metal oxide (NiO-MnO2).

The rGO from GO was prepared individually to check the electrochemical performance of bare
rGO in comparison with other prepared nanomaterials. However, the rGO synthesis process was
done by the reduction of GO solution using hydrazine hydrate as a reducing agent. The chemical
conversion involving the brownish GO solution into black rGO solution confirmed the formation
of rGO sheets [9,10]. To incorporate multiple metal oxides into these rGO layers, two approaches

24
CHAPTER 3

were taken under consideration. Firstly, the direct mixing of rGO nanosheets with the already
prepared NiO-MnO2 nanoparticles was done by ex-situ mixing process. The process is called the
ex-situ synthesis process because of it involved the mixing of two already prepared (NiO-MnO2,
rGO) materials in the vicinity of the reaction process. The rGO layers were expected to be mixed
with NiO-MnO2 mixed nanoparticles and to be incorporated in between the rGO layers as well as
on its surface. Usually, the chemically reduced rGO possesses negative zeta potential on its surface
and hence it tends to attract the positively charged cations [11.12]. Based on this point, the
homogeneously dispersed rGO was mixed in an ex-situ process to prepare NiO-MnO2-rGO
nanomaterial.

But, the intercalation of metal oxide nanoparticles in between the rGO layers by the ex-situ process
is always inefficient because of the high agglomeration properties of rGO layers [13]. Once the
rGO layers are stacked together, the allowed interlayer distance between the rGO layers becomes
decreased [14]. So, it is a highly likely possibility that the external rGO surface area could only be
covered by the incorporated metal oxide nanoparticles (NiO-MnO2) instead of interlayers. Even if
some particles entered into the layers, the amount should be very lower. As a consequence of this
phenomenon, the defective sides and pores of the bare rGO could be blocked by the incorporated
metal oxides [15]. So, it is almost impossible to get a hierarchal composite of metal oxides and
rGO by adopting an ex-situ mixing process.

To overcome this problem, the incorporation of metal oxides or hydroxides in rGO layer was done
by an in-situ synthesis process in the synthesis of Ni(OH)2-MnO2-rGO. The in-situ synthesis
process involved the tricky mixing of precursors with GO solution mentioned in section 2.6. In
our case, the one-step gel formation reaction between KMnO4 and glycerol initially provided a
cross-linked network with the GO layers. The nickel nitrate was expected to remain stable during
the mixing process in the in-situ process. As the total mixing procedure was done in solution form,
the formation and growth of metal oxides or hydroxides were expected to be occurred on and in
between the rGO layers. However, the ultimate phase transformation of manganese oxide and
nickel hydroxide nanoparticles was expected to have occurred during the 24 hours of hydrothermal
growth. It is assumed that at 180 °C, (1) the glycerol reacted with NO3- and released hydroxyl (OH-
) ions (equation 2), which reduced the Ni(NO3)2 to form Ni(OH)2 on and in between the rGO layers;

25
CHAPTER 3

and (2) cross-linked network of manganese with glycerol fragments was firstly converted into
manganese hydroxide and upon reaction with oxygen, it finally converted into stable MnO2.

4 C3H8O3 + NO3− → 4 C3H6O3 + NH3 + OH− + 2 H2O (2)

The confirmation of the intercalated manganese oxide and nickel hydroxide nanoparticles was
further done by XRD and presented in the Figure. 3.10.

3.2 Electrochemical and capacitive performance

3.2.1 Cyclic Voltammetry and Galvanostatic Charging-Discharging

Manganese oxide is prominent for its multivalent oxidation state [16]. The multivalent state
facilitates the pseudocapacitive performance during the electrochemical redox reactions. Besides
the large surface area ensures good EDLC formation in the accessible surface of the electrode. In
Figure 3.2 (a) the detailed Cylcic Voltammogram (CV) and Galvanostatic Charging and
Discharging (GCD) of manganese oxide are shown. Different scans rate shows different current
response in between 0.0 to +0.6 V. Usually, the higher scan rates show more current response and
high specific capacitance. The highest capacitance was found 66.67 Fg-1 at 1.0 Ag-1 current density.
Usually, the proper window selection was necessary by using aqueous Na2SO4 as electrolyte
because of its limited working potential and usually it possesses lower energy density. But, the
conductivity value of aqueous Na2SO4 is satisfactory due to the high dielectric constant of the
Na2SO4 [17]. So, the energy density as calculated from equation (4) and (5) was found 0.83 Whkg-
1
with a power density 150 Wkg-1. This performance was satisfactory but not compatible enough
for being a standard supercapacitor electrode material. The limited window (+0.6 V) as shown in
figure 3.2(a) might be responsible for laser energy density. So, the incorporation of another metal
oxide was adopted in the next step to enhance the electrochemical working potential.

For a typical two-electrode cell setup as shown in section 2.4, the specific capacitance was
calculated by using the equation (3) and consecutively the energy and power density were
calculated by using the equation (4) and (5).

𝐼.∆𝑡
Csp = 2 (3)
𝑚.∆𝑉

26
CHAPTER 3

Where, I = applied current on the active material, ∆𝑡 = Discharge time, m = Active mass on each
electrode, ∆𝑉= working potential window.

Csp .∆𝑉 2
𝐸= (4)
8

𝐸
P= (5)
∆𝑡

The incorporation of another metal oxide into the manganese is always an attractive technique to
enhance the capacitive performance rather than neat manganese oxide alone. This allows the
enhancement of the total active surface area to store the electrical charges [18]. More specifically,
this enhanced surface area facilitates the window expansion which ultimately results in higher
specific capacitance and higher energy density [19]. In Figure 3.2 (b), the electrochemical
performance of NiO incorporated MnO2 was evaluated. In this case, the current response in the
cyclic voltammetry was higher than neat MnO2.
(a)

(b)

Figure 3.2 (a) CV and GCD of neat MnO2 and (b) CV and GCD of NiO-MnO2

27
CHAPTER 3

A little expansion of +0.1 V in the potential window compared to manganese oxide nanoparticles
(+0.6 V) can be observed due to the synergistic effect of NiO present in NiO-MnO2 nanoparticles.
Hence, the specific capacitance was found to be 94.29 Fg-1 at 1 Ag-1 using 0.5 Na2SO4.
Subsequently, the energy density was calculated and found to be 1.60 Whkg-1 with 175 Wkg-1
power density. The higher capacitive properties of NiO-MnO2 in comparison with MnO2 can be
explained from the Figure 3.2 (a) and (b). Usually, the expanded window provides extra active
surface area under the curve of CV which means the larger amount of charge accumulation when
charging of the material occurs [20,21].

However, in the enhancement of the energy density, the as prepared metal oxides alone are not
sufficient enough to meet the commercial demands of energy storage devices [23,24]. Usually the
incorporation of carbonaceous materials like rGO with metal oxides is the first choice. The
electrochemical performance of bare rGO is presented in Figure 3.3. In this study, reduced
graphene oxide was incorporated by both in-situ and ex-situ methods. The ex-situ process resulted
in NiO-MnO2- rGO and the in-situ process resulted in the product Ni(OH)2-MnO2-rGO. The
detailed electrochemical evaluation of NiO-MnO2-rGO and Ni(OH)2-MnO2-rGO are shown in
Figure 3.4 (a) and (b) respectively.

Figure 3.3 CV and GCD of rGO synthesized by modified Hummers method.

In the case of rGO, the current response from CV showed in Figure. 3.3 was pretty impressive and
that exhibited a larger (+0.9 V) potential window than neat MnO2 and NiO-MnO2. That might
happen because of the larger available surface area for charge accumulation [25]. The almost

28
CHAPTER 3

perfect EDLC shape indicates the highly conductive and capacitive nature of synthesized rGO. In
the case of rGO, the specific capacitance was found to be 186.67 Fg-1 at 1.0 Ag-1 using 0.5 M
Na2SO4 (showed in Figure 3.3). The energy and power density of rGO was 5.25 Whkg-1 and power
density was found 225.0 Wkg-1 at 1 Ag-1 current density. In the fabrication of a composite, this
rGO was firstly mixed with the previously synthesized NiO-MnO2 directly by adopting the ex-situ
process. The resulting ex-situ process yields unexpected result. The electrochemical performance
of NiO-MnO2-rGO is shown in the Figure 3.4 (a). The current response of the ex-situ composite
was even poorer than neat rGO. That might have happened because of the blocked nanostructures
that hinder the natural conductivity of rGO sheets.
(a)

(b)

Figure 3.4 (a) CV and GCD of NiO-MnO2-rGO (ex-situ synthesis process) and (b) CV and GCD of
Ni(OH)2-MnO2-rGO in situ synthesis process.

29
CHAPTER 3

The blocked structures here are defined as the disoriented metal nanoparticle dispersion in the rGO
sheets during the synthesis procedure of ex-situ. The performance of this ex-situ product was 95.00
Fg-1 at 1.0 Ag-1 using 0.5 M Na2SO4. The energy density was also laser than rGO and that is almost
2.11 Whkg-1 with the power density of 200.0 Wkg-1 in between a potential window of (0.8V). So,
in our case this was an unsuitable approach for synthesizing a nanoparticle by just mixing it with
graphene solution. However, besides the ex-situ process, the literature has also emphasized the in-
situ growth formation of metal oxides and hydroxides in the rGO layers to prepare hybrid materials
for supercapacitors [26-28].

In the in-situ incorporation of metal oxides, the hydrothermal growth of Ni(OH)2 and MnO2 were
taken place in the rGO layers and resulted in Ni(OH)2-MnO2-rGO. The specific capacitance was
found maximum for Ni(OH)2-MnO2-rGO composite (320 Fg-1 at 1 Ag-1). The energy and power
density of Ni(OH)2-MnO2-rGO was found 11.11 Whkg-1 and 250 Wkg-1 at 1 Ag-1 current density.
The self-oriented growth formation of α-Ni(OH)2 and γ-MnO2 with granular shape formation
enhanced the surface area and interlayer distance between the rGO layers. The metal oxides and
hydroxides growth formation also contribute to the self-assembly among closer rGO layers [29].
This nanostructure is suitable for the mobility of counter ions during the potential difference
applied [30]. The potential window was achieved +1.0 V for the composite of Ni(OH)2-MnO2-
rGO and here presented in Figure 3.4 (b). The expansion of the window is might be occurred due
to the growth of granular-shaped self-oriented Ni(OH)2 and MnO2 spheres which allow
accumulating sufficient charge within a large window by maintaining high conductivity and
mobility.

The electrochemical performance of all the synthesized material was performed using 0.5 M
Na2SO4 electrolyte and collectively showed in Figure 3.5. In Figure 3.5 (a), the cyclic voltammetry
of all synthesized materials (MnO2, NiO-MnO2, NiO-MnO2-rGO, rGO, and Ni(OH)2-MnO2-rGO)
is being shown at 20 mVs-1 scan rates. From this comparative study, it can be appearing that the
current response of Ni(OH)2-MnO2-rGO is maximum compared to others. As well as the working
potential window of the Ni(OH)2-MnO2-rGO is higher than others. Usually, the perfect rectangular
shape indicates the best EDLC layer formation during the electrochemical reactions.
Pseudocapacitive peaks are invisible in the CV and GCD curves of Figure. 3.4 mainly because of
low proportion of metal oxides or hydroxides are present in the final composite. The proportions

30
CHAPTER 3

are described in the elemental analysis section. As well as the aqueous electrolyte is less active to
the redox reactions of metal nanoparticles than alkaline solutions.

Figure 3.5 (a) Comparison of Cyclic voltammetry curve of (MnO2, NiO-MnO2, NiO-MnO2-rGO, rGO, and
Ni(OH)2-MnO2-rGO). (b) Comparison of Galvanostatic charging and discharging curve of (MnO2, NiO-
MnO2, NiO-MnO2-rGO, rGO, and Ni(OH)2-MnO2-rGO)

From the Figure 3.5 (b), the specific capacitance for (MnO2, NiO-MnO2, NiO-MnO2-rGO, rGO,
and Ni(OH)2-MnO2-rGO) has been shown and can be calculated by using discharging time.
(a) (b)

Figure 3.6 (a) Ragone plot for comparing the supercapacitor performance of synthesized materials. (b)
Variation of specific capacitance with various current densities.

31
CHAPTER 3

Table 1. Summarized electrochemical performance of (MnO2, NiO-MnO2, NiO-MnO2-rGO, rGO,

and Ni(OH)2-MnO2-rGO).

Current Specific Energy Power

Materials Density, Capacitance, Density, Density,
Ag-1 Fg-1 Whkg-1 Wkg-1

1.0 66.67 0.83 150.00

MnO2 2.0 53.33 0.67 300.00

4.0 26.67 0.33 600.00

1.0 94.29 1.60 175.00

NiO-MnO2 2.0 68.57 1.17 350.00

4.0 45.71 0.78 700.00

1.0 186.67 5.25 225.00

rGO 2.0 133.33 3.75 450.00

4.0 106.67 3.00 900.00

1.0 95.00 2.11 200.00

NiO-
MnO2- 2.0 80.00 1.78 400.00
rGO
4.0 50.00 1.11 800.00

1.0 320.00 11.11 250.00

Ni(OH)2-
MnO2- 2.0 264.00 9.17 500.00
rGO
4.0 200.00 6.94 1000.00

32
CHAPTER 3

In Figure 3.6 (a), the comparison of energy density VS power density has been presented. From
this demonstration, it can be clearly stated that the hybrid composite of Ni(OH)2-MnO2-rGO has
achieved the attributes required for being a competent supercapacitor material. In Figure 3.6 (b),
it could be observed that with the variation of current density, the specific capacitance decreases
significantly. These results reveal the superiority of Ni(OH)2-MnO2-rGO as applicable
supercapacitor material. The summary of the total electrochemical performance of this research is
presented in Table 1.

3.2.2 Impedance analysis

In electrochemical impedance spectroscopy (EIS), the Nyquist plots are composed of an obvious
semicircle in the high-frequency region and a straight line in the low frequency [31]. The intercept
of the semicircle at the real axis (Z’) can be applied to characterize Rs (ohmic resistance) from the
electrolyte, electrode material, and some other possible ohmic resistances between the working
electrode [32].

Figure. 3.7 EIS of (MnO2, NiO-MnO2, NiO-MnO2-rGO, rGO, and Ni(OH)2-MnO2-rGO)

The electrochemical impedance of (MnO2, NiO-MnO2, NiO-MnO2-rGO, rGO, and Ni(OH)2-MnO2-

rGO) electrodes was examined over the frequency range of (105 to 0.01) Hz in 0.5 M Na2SO4. In

33
CHAPTER 3

Figure. 3.7, the solution resistance values for Ni(OH)2-MnO2-rGO were found least compared to
others. The Rs and Rct values of all materials are presented in the Table 2. The Rs value for this
composite was found 4.7 Ω. In the case of MnO2, the solution resistance value was maximum due
to less conductivity and wettability in the solid electrolyte interface of metal manganese oxides
The reason behind the less solution resistance of Ni(OH)2-MnO2-rGO must be related to its hybrid
nanostructure. The pseudocapacitive nanoparticles growth on the assembled rGO layer provides an
outstanding synergy that enhances the overall conductivity of the electrode. Hence, the charge transfer
resistance or Rct was found at 12.2 Ω and which was minimum for Ni(OH)2-MnO2-rGO hybrid composite.
Rct, denoted as the charge transfer resistance, is relevant to the diameter of the semicircle, which originates
from the redox reactions occurring between the electrode and the electrolyte [33]. This should be
attributed to the great reduction in the transportation path of active ions resulting from the increase
in specific surface area. ZW demonstrates the Warburg impedance, which is connected with the
slope of the straight line [34].

Table 2. Summary of the Rs and Rct values for the synthesized nanomaterials.

NiO-
Unit MnO2 NiO-MnO2 MnO2- rGO Ni(OH)2-MnO2-rGO
rGO

Rs(Ω) 13.5 12.5 11.3 6.2 4.7

Rct (Ω) 45.2 30.8 42.4 22.6 12.2

Cdl (µF) 6.54×10-6 2.98×10-5 2.32×10-5 1.32×10-4 3.4×10-2

Cp (µF) 0.006258 0.00857 0.02516 0.01285 0.03562

W
0.005687 0.008575 0.005896 0.006354 0.008956
(cm2/s)

This value can be used to characterize the diffusion rate of the active ions stored and release during
the charging-discharging process. Cdl and Cp corresponds to the double layer capacitance and
pseudocapacitance of the circuit elements respectively. So, the RC circuit fitting reveals that

34
CHAPTER 3

Ni(OH)2-MnO2-rGO is superior among other synthesized nanomaterial when using 0.5 M Na2SO4
as electrolyte.

3.2.3 Cyclic Stability

Cyclic stability or electrochemical cyclic stability of an electrode material means the continuous
investigation of the electrochemical performance including the initial capacitance retention as well
as coulombic efficiency under the working potential with a high current density. Again, the
Coulombic efficiency (η) is the ratio of discharge capacity to charge capacity within the same
cycle. To determine the stability of the Ni(OH)2-MnO2-rGO material-based device, the symmetric
cell with 0.5 M Na2SO4 was subjected to 2000 consecutive GCD cycles within the potential range
(0.0 to 1.0) V at a fixed current density of 10 Ag-1. The stability of the device is presented in Figure.
3.8 with the variation of columbic efficiency as the function of the number of cycles. After 2000
cycles, Ni(OH)2-MnO2-rGO electrode samples in 0.5 M Na2SO4 electrolyte demonstrated a
coulombic efficiency of 97% of its initial. The layered structure of the Ni(OH)2-MnO2-rGO
experienced a very insignificant structural change in the neutral electrolyte medium. It reflected
the long-term durability of the material. Usually, the neutral electrolytes are superior for their
nondestructive action towards the electrode materials during the electrochemical process [35,36].

Figure. 3.8 Cyclic stability test of Ni(OH)2-MnO2-rGO composite at a current density of 10 Ag-1.

The high percentage of coulombic efficiency was also attributed to the easy and highly accessible
interconnected layers that facilitate retaining stability after a long cycle of the Ni(OH)2-MnO2-
35
CHAPTER 3

rGO. The capacitance retention and coulombic efficiency was calculated by using equation (6) and
(7) respectively.

n′ th cycle capacitance
Capacitance retention = ×100 % (6)
1′ st cycle capacitance

tdischarge
Coulombic efficiency, η = × 100% (7)
tcharge

The first five cycles showed 100 % coulombic efficiency with 100 % capacitance retention and
the last five cycles showed 97% coulombic efficiency with 90% capacitance retention. The highly
retainable capacitance performance might attribute to the well-defined stable layered structure
through which the electrolyte ions can move easily without interrupting the nanostructures. This
result suggests the long-term applicability of the as-prepared Ni(OH)2-MnO2-rGO composite in
the fabrication of a real-time supercapacitor.

3.2.4 Active mass variation and GO weight optimization

To evaluate the specific capacitance of the prepared nanomaterials more clearly, the electrodes
with different mass loading were applied to investigate by GCD method in 0.5 M Na2SO4 solution
within their appropriate voltage window at 1 Ag-1 current density.
(a) (b)

Figure 3.9 (a) Variation of specific capacitance with different mass loading and (b) variation of specific
capacitance with the variation of the amount of GO required during the preparation.

36
CHAPTER 3

The results showed in Figure 3.9 (a) suggest that the prepared nanomaterials exhibited different
capacitive behavior with increasing active mass loading. The specific capacitance calculated from
the GCD curves of MnO2 at 1 Ag-1 decreased from 66 Fg-1 to 8 Fg-1 with increasing mass from 0.5
to 3.0 mgcm-2 in electrode while for NiO-MnO2, the specific capacitance decreased significantly
with increasing mass from 0.5 to 3 mgcm-2 in electrode under the same experimental condition. In
the case of, NiO-MnO2-rGO, rGO, and Ni(OH)2-MnO2-rGO, the optimum mass loading and
maximum performance were found at 2 mgcm-2. The decrease in capacitance value with increasing
mass loading is due to the larger electrochemical resistance and low ions diffusion in solid
electrolyte interface with high mass loading [37,38]. With increasing mass loading, the thickness
of the electrode is increased. Hence, it can be speculated that a longer distance of ionic motion in
the lower mass loaded electrode is necessary from the electrolyte to the inner portion of the
nanomaterials. In the range of the applied current densities, alkali cations have enough time to
reach the surface of nanomaterials for the lower mass loaded electrode for its thin thickness. Hence,
the absorption/desorption reaction can occur favorably. A thin layer of electrode coating usually
exerts high capacitance, but this is not always applicable for commercial implications. For a proper
mass loading, the diffusion of ions from electrolyte can gain access to almost all available pores
of the electrode at low current densities, leading to a complete insertion reaction, and therefore, it
shows almost ideal capacitive behavior [39,40]. Thus proper optimization of mass loading is
necessary for achieving the maximum performance of electrode materials.

The GO amount also plays an important role in the morphological control of the hybrid spheres.
The high oriented growth and aggregation ability Ni(OH)2and MnO2 nanoparticles on and between
rGO surface were found for 2.0 g GO during the synthesis of the Ni(OH)2-MnO2-rGO. Because,
with this amount of GO, the best performance was achieved. As the GO amount increased from
0.05 g to 0.5 g, the structural changes might have occurred during the hydrothermal formation
process. It is assumed that up to 2.0 g of GO, the assembled structures increased in size and then
began to become round showed in Figures 3.11 (b). However, further increasing the GO amount
might lead to the disintegration of spherical structure, and even the self-aggregation of graphene
nanosheets. Hence, it is attributed to lower performance as showed in Figure 3.9 (b).

37
CHAPTER 3

3.3 Structure, Morphology and Elemental analysis

3.3.1 Structure and Surface Morphology Analysis

XRD was conducted to understand the geometry and chemical structure of the as-prepared MnO2,
NiO-MnO2, and Ni(OH)-MnO2-rGO composite. the XRD result of neat MnO2 astonishingly
showed us the coexistence of MnO2 and Mn2O3 nanoparticles. Hence, in Figure 3.10, the neat
manganese oxide is attributed as MnXOY instead of MnO2. Similarly, in the XRD result of NiO-
MnO2 sample, the binary oxide of manganese is present. So, it has also presented as NiO-MnXOY
instead of NiO-MnO2 in the Figure 3.10. But, the composite synthesized in the hydrothermal
process resulted in the formation of α-Ni(OH)2 and γ-MnO2 on the rGO layers.

Figure 3.10 XRD patterns of MnXOY, NiO-MnXOY, and Ni(OH)-MnO2-rGO composite.

38
CHAPTER 3

For MnXOY, the prominent peaks observed at 2θ of 32.9°, 38.3°, 45.3°, 49.3°, 55.4°, and 66.2° can
be indexed as (111), (200), (220), (311), (222), and (400) (JCPDS 41-1442) indicate the presence
of Mn2O3 [19]. Additionally, the peaks observed at 2θ of 12.7°,18.1°, 28.8°, 37.5°, 42.1°,
49.9°,56.2°,60.3°, can be indexed as (110), (200), (310), (211), (301), (411), (600), and (521)
planes of tetragonal MnO2 (JCPDS 44-0141), confirmed the presence of MnO2 in the MnXOY [41].
It is revealed that multiple phases of manganese oxides, both Mn2O3 and MnO2 are present on the
prepared MnXOY. In the XRD pattern of mixed oxide (NiO-MnxOY), the peaks appeared at 2θ of
37.2°, 43.1°, 62.9°, 75.4°, 79.4° resulted from the diffractions of (111), (200), (220), (311) and
(222) planes of cubic NiO (JSPDS card no. 71-1179) [42]. The rest of the peaks has been
designated for MnXOY in the NiO-MnXOY mixed oxides. The crystal lattice structure of tetragonal
MnO2 with a lattice constant of a = 4.3950 Å, c = 2.8600 Å, and cubic Mn2O3 with a lattice constant
a= 9.41000 Å have been identified in both MnXOY and NiO-MnXOY. Hence, multivalent
manganese is present in MnXOY and NiO-MnXOY. Here, a slight shifting in the peak's location has
been observed for MnO2 and Mn2O3 in NiO-MnXOY which might have occurred for the co-
existence of two or more planes NiO and MnXOY at a time.

The XRD patterns show that the well-defined diffraction peaks of Ni(OH)2-MnO2-RGO can be
successfully indexed to the α-Ni(OH)2 phase (JCPDS 38-0715), γ-MnO2 phase (JCPDS 14- 0644),
and the AB stacking order of graphene sheets (10.4°, corresponding to the interlayer spacing of
0.85 nm. The morphology of synthesized neat MnXOY and NiO-MnXOY mixed oxide was
investigated by FESEM. The SEM images are shown in Figure 3.11 (a) indicated that MnXOY is
capsule-shaped with an average diameter of 71 nm. However, in Figure 3.11(b) rod-shaped mixed
oxide with an average diameter of 89 nm and length of 0.66 μm was evident from the image of
NiO-MnXOY.

Self-aggregation of oxides is evident for the capsule-shaped MnXOY particles. Interestingly, the
self-aggregations have been prevented by the occurrence of randomly ordered rod-shaped NiO
nanoparticles in NiO- MnXOY matrix. It is expected that the homogeneous heating contributed to
the formation of a highly crystalline NiO rod in between MnXOY nanoparticles. A well- connected
nanostructure of NiO- MnXOY nanoparticles has been formed by the anisotropic growth of NiO
nano-rods over the surface of MnXOY nanoparticles.

39
CHAPTER 3

Figure. 3.11 (a) SEM image of capsule shaped MnXOY (b) SEM image of rod shaped NiO in MnXOY and
(c,d,e,f) SEM images of Ni(OH)2-MnO2-rGO.

In Figure 3.11 (c, d), the growth of granular shape α-Ni(OH)2 and γ-MnO2 on the rGO layers are
visible. This growth formation of Ni(OH)2 mainly occurs during the high-temperature
hydrothermal treatment of Ni(NO3)2 with mild glycerin agent glycerin. At 180 °C, GO is reduce

40
CHAPTER 3

to rGO by reacting with glycerol [43]. The growth formation could have occurred in three stages
(i) glycerol and NO3- undergo a redox reaction releasing hydroxyl (OH-) ions under 180 °C, (ii)
the Ni2+ ions from the Ni(NO3)2 solution and Mn2+ ions from the cross-linked matrix might react
with OH− ions to form Ni(OH)2 and Mn(OH)2; and (iii) at 180 °C the Mn(OH)2 might be converted
to stable MnO2 upon reaction with oxygen [44,45].

Figure 3.12 Red circles denote the presence of Ni(OH)2 and green circles denote the MnO2.

Because of the hydrogen-bonding interactions between MnO2 and Ni-(OH)2 primary

nanoparticles, MnO2 primary nanoparticles may disorderly stack with Ni(OH)2 primary
nanosheets and grow along with rGO to form a hybrid nanosheet. From the SEM image in Figure
3.11 (e,f), it is seen that the spherical growth of Ni(OH)2 and MnO2 assembled with rGO sheets
occurred as expected on and in between the rGO layers. These nanosheets of rGO tend to aggregate
perpendicular to the surface planes to decrease the surface energy by reducing exposed areas.
Therefore, as the reaction proceeds, spontaneous energy-minimizing self-assembly of the resulting
hybrid nanosheets would occur, producing spherical and layered self-assembled structures [46,47].

41
CHAPTER 3

3.3.2 Elemental Analysis

Elemental analysis of the Ni(OH)2-MnO2-rGO nanocomposites has been performed by Energy

Dispersive X-ray (EDX) method. In Figure 3.13, the peaks observed at 0.277, 0.523, 5.898, and
8.040 keV, for K lines of C, O, Mn and Ni respectively. So, the EDX data confirms the presence
of required elements in synthesized nanocomposites. The EDX result showed the amount of
manganese and nickel present in rGO layers concerning carbon and oxygen is very little (C = 79
% O = 8% , Mn = 10%, Ni = 3%) As well as the absence of any foreign elements in the sample
confirms the purity of the as-prepared Ni(OH)2-MnO2-rGO. However, the result also suggests that
the number of metal nanoparticles can be tuned in future work to check whether the performance
of the composite will enhance or not.

Figure. 3.13 EDX spectra of Ni(OH)2-MnO2-rGO

3.3.3 Functional group analysis

Fourier-Transform Infrared Spectroscopy (FT-IR) spectroscopy relies on the fact that most
molecules absorb light in the infra-red region of the electromagnetic spectrum. This absorption
corresponds specifically to the bond present in the molecule. The frequency range is measured as
wave numbers over range (400-4000 cm-1) [48]. FT-IR spectroscopy has characterized, to confirm

42
CHAPTER 3

the functional groups present in synthesized compounds showed in Figure 3.14. Two strong
stretching vibration bands appeared at 532 and 590 cm-1 confirmed the formation of NiO-MnXOY
mixed oxide. The peak around 532 cm-1 ascribed to Mn-O vibrations in MnXOY [49]. Besides,
absorption bands that appeared at 1624 and 1101 cm-1 have been assigned to bending vibrations
of (O-H) combined with the Mn atoms [50]. The broad peaks appeared at 3448 and 3441 cm-1
attributed to O-H stretching vibrations in the MnXOY and NiO-MnXOY respectively. It indicates
the presence of hydrated water molecules in the prepared materials.

Figure 3.14 FT-IR spectra of Ni(OH)2-MnO2-rGO, MnXOY and NiO-MnXOY.

The characterization peaks for Ni(OH)2-MnO2-rGO show that the characteristic band of the
carboxyl group appears at 3441 cm-1 (O-H stretching vibration), 1720 cm-1 (C=O stretching
vibration), 1605 cm-1 (skeletal vibrations from un-oxidized graphitic domains), 1387 cm-1 (O-H
deformations in the C-OH groups), 1231 cm-1 (C–OH stretching vibration) and 1034 cm-1 (C-O

43
CHAPTER 3

stretching vibration in C-O-C in epoxide). However, the strong absorption at 521 cm-1 is due to
(Ni-O-H) bending and Ni-O stretching vibrations in the composite. The peaks that appeared around
1407 and 735 cm-1 are attributing the vibrations of the O-Mn-O bond of MnO2. From that
investigation, it is pretty clear that the expected functional groups are present in the Ni(OH)2-
MnO2-rGO composite.

44
CHAPTER 3

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CHAPTER 4
CONCLUSIONS AND FUTURE ASPECTS

4.1 Conclusion

The mixed oxide of manganese nanoparticles (MnXOY), NiO-doped mixed manganese

nanoparticles (NiO-MnXOY) and Ni(OH)2-MnO2-rGO were successfully prepared by adopting a
facile gel formation technique. The multivalent metal oxides and hydroxides in the composite were
identified with distinctive surface morphology and nanostructure. The formation of spherical
Ni(OH)2 and MnO2 in the self-assembled rGO layers is responsible for the enhancement of
capacitive properties in Ni(OH)2-MnO2-rGO hybrid composite. The composite demonstrated a
moderately high Csp of 320 Fg-1 at 1.0 Ag-1 with outstanding energy density (11.11 Whkg-1) and
power density (250 Wkg-1) in 0.5 M Na2SO4 electrolyte. The performance was rationalized with
other synthesized nanomaterials. The synergistic effect of Ni(OH)2 and MnO2 with rGO layers
facilitates a high ion conductivity and inter-connectivity which was responsible for the superior
performance of the material as a supercapacitor. The obtained results of this research will help to
adopt sustainable technology for industries by improving the manufacturing process of
supercapacitor materials.

4.2 Future aspects of this research

Though this work demonstrated an effective pathway to design and fabrication of advanced
electrode materials of Ni(OH)2-MnO2-rGO, still it has many scopes to be developed. Especially,
the agglomeration of the metal oxides can be reduced by using a capping agent like CTAB, PEG,
PVP, etc. Moreover, the electrolyte design will be an attractive option for enhancing the charge
storing performance in the fabricated electrode material. As well, the incorporation of other metal
oxides or hydroxides into the rGO layers can enhance the overall performance which could be
useful for the next-generation practical supercapacitor device.

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