1

National Institute of Technology Warangal

Internship Report on

Nitrogen-doped Ni-MOF
co-doped with
Mxene/Graphene for
supercapacitor
applications

UNDER THE GUIDANCE OF

Dr. P. Sampath Kumar

Submitted By:

A.Ravivarma
K.Abhijith
M.DineshVenkat
Md.Musharraf Ismail

-pg. 1
 2

CERTIFICATE

This is to certify that the internship report entitled is a bonafide record of

work carried out by “Md.Musharraf Ismail(21CHB0B33),
M.DineshVenkat(21CHB0B34),K.Abhijith(20CHB0B062),
A.RaviVarma(21CHB0B09) ” submitted to the “Department of
Chemical Engineering”, in partial fulfillment of the requirements for the
award of the Degree of Bachelor of Technology in “Chemical
Engineering” at National Institute of Technology, Warangal.

Dr. P. Sampath Kumar

Assistant Professor
Department of Chemical Engineering
NIT Warangal

-pg. 2
 1

ACKNOWLEDGEMENT

We would like to express our deepest gratitude to our Internship guide,

“Dr. P. Sampath Kumar”, for agreeing to be our guide and supervisor for this Internship
on the topic “Nitrogen-doped Ni-MOF co-doped with Mxene/Graphene for
supercapacitor applications”, for his guidance and support which helped us in
developing this internship as well as collaborating throughout the Internship duration.
It was a fruitful experience to have done the Internship under such a reputed professor,
who helped us with his ideas, criticisms, and thought processes.

We would also like to give our special thanks to B. Dinesh, for giving us
the opportunity to do this Internship. It was a great learning experience
in the field of chemical research.

-pg. 1
 2

CONTENTS

1. Abstract…………..... 2-3
2. Motivation……………..3
3. Introduction……………3-8
4. Literature…………..... 8-12
5. Materials and Methods……….12-15
Materials
Experimental procedure
6. Result and Analysis………….....15-42
7. Conclusion ………….....42-43
8. References………….....43-44

1. ABSTRACT

The search for new materials and techniques in the realm of

supercapacitor technology has escalated due to the demand for high-
performance energy storage devices. The tunable porosity and variety of
metal centers of metal-organic frameworks (MOFs), one of these, have made
them stand out as attractive options. For use in practical applications,
however, pure MOFs must be improved because to their inherent drawbacks,
including limited electrical conductivity and low capacitance.

This study offers a ground-breaking method for improving MOFs'

supercapacitive performance with the addition of MXene nanosheets and
RGO. The excellent electrical conductivity and large surface area of
-pg. 2
 3

MXenes, a family of two-dimensional transition metal carbides or nitrides,

are well known. A number of doped MOFs were successfully created by
integrating in a synergistic manner the special qualities of MOFs with
MXenes and Graphene in a simple and scalable way.

2. MOTIVATION

The electrochemical performance of supercapacitors can be tailored by

researchers using the hydrothermal approach to synthesis doped MOFs using
MXene or graphene, bringing up new uses for energy storage. By combining
conductive nanoparticles with MOFs, it is possible to address the energy
needs of contemporary civilization, promote sustainable technologies, and
hasten the transition to a cleaner and more efficient energy system.

3. INTRODUCTION
Rising energy demand, increasing integration of renewable energy, and the
need to reduce greenhouse gas emissions have made energy storage of paramount importance.

The energy storage technology that fills the space between conventional capacitors and
batteries is known as a supercapacitor, often referred to as an ultracapacitor or an
electrochemical capacitor. High power density, quick charge and discharge speeds, and long
cycle life are all features they provide. Supercapacitors are divided into different categories
according to their working voltage, electrolyte composition, and electrode material. ( Electric
Double-Layer Capacitors (EDLCs),Pseudocapacitors,Hybrid Supercapacitors etc .).

Supercapacitor classification offers a framework for comprehending their performance traits

and appropriateness for various applications. Supercapacitor technology is currently
undergoing research and development with the goal of increasing energy density, extending
cycle life, and enhancing overall performance to enable their incorporation into a variety of
energy storage systems

-pg. 3
 4

Researchers are actively studying different synthesis methods, electrode structures and
electrolyte systems to optimize the performance of MOF-based supercapacitors. The goal is to
achieve higher energy densities, faster charge/discharge rates, and improved overall device
performance. Although challenges remain, MOF's unique properties make it a promising
candidate for next-generation supercapacitors for applications such as portable electronics,
electric vehicles, and renewable energy systems.

Metal Organic Frameworks (MOFs) :

A type of porous materials known as Metal-Organic Frameworks (MOFs) is made up of metal

ions or clusters that have been coordinated with organic ligands. They are often referred to as
porous coordination networks or coordination polymers. MOFs display a crystalline structure
with a large amount of surface area and clearly defined nanometer-sized holes. Because of
their distinctive structure, MOFs have extraordinary qualities that make them desirable for a
variety of applications in diverse industries.

Different mechanisms, such as solvothermal reactions, hydrothermal reactions, and

mechanochemical processes, can be used to create MOFs. In order to enhance the creation of
the desired MOF structure, these techniques entail combining metal ions or clusters with
organic ligands in an appropriate solvent or under particular circumstances. The characteristics
and capabilities of the resulting MOF are determined by the metal ions and ligands used.

The porous structure of MOFs is one of their distinguishing features. MOF pores can be
divided into two categories: permanent pores and non-permanent pores. Metal ions and organic
ligands are arranged to form permanent pores, which continue to exist long after the presence
of visitor molecules has been eliminated. However, the presence of visitor molecules causes
non-permanent pores to develop.

The huge surface area of MOFs in supercapacitors is one of its main advantages. There are
plenty of sites for the adsorption and storage of ions in MOFs, which can have surface areas
per gramme ranging from hundreds to thousands of square metres. improved energy storage
-pg. 4
 5

capacity in supercapacitors is made possible by this feature's improved charge storage

capacity. Fast ion diffusion is also made possible by the huge surface area, which enhances
charge-discharge rates and overall performance.

Due to their usual low electrical conductivity, MOFs may not be suitable for use as effective
electrode materials in supercapacitors. Low conductivity can lead to excessive internal
resistance, which lowers the supercapacitor's overall performance and power output. When
exposed to water or aqueous electrolytes, many MOFs can degrade or undergo structural
changes. Due to the safety and environmental benefits of aqueous-based supercapacitors, this
restricts their application in such devices. The supercapacitor's lifespan and performance may
be affected by the instability. Although MOFs have large surface areas and pore volumes,
they often have lower energy densities than other electrode materials like carbon-based
materials or transition metal oxides (the amount of energy stored per unit mass or volume).
Their use in high-energy-density supercapacitors, which are necessary for several applications,
is hampered by this constraint.
Despite these drawbacks, research is still being done to solve these problems and enhance the
performance of MOF-based supercapacitors. To get beyond these restrictions and realise
MOFs' full potential in energy storage applications, techniques like doping MOFs with
conductive materials, creating novel MOF structures, and investigating hybrid electrode
topologies are being investigated.

A description of MXenes :

MXenes were initially identified in 2011 and are a class of 2D transition metal carbides,
nitrides, and carbonitrides. In the layered ternary compounds known as MAX phases, M
stands for an early transition metal, A for an element from Group 13 or 14, and X for
carbon and/or nitrogen, they are generated from. The A element in MAX phases is
selectively etched to create MXenes, which have a layered structure with a large surface
area and great electrical conductivity.
Expanding our knowledge of MXenes' characteristics, creating scalable synthesis
techniques, investigating novel functionalizations, and increasing their potential for use
-pg. 5
 6

are the main goals of current research. MXenes continue to pioneer the way for
improvements in energy storage thanks to their amazing mix of electrical conductivity,
high surface area, and chemical stability.

MXenes' advantages in supercapacitors

High conductivity: The metallic conductivity of MXenes makes charge transport into
supercapacitor electrodes efficient. Rapid charge and discharge rates are made possible by
this property, which improves power density.

Large Surface Area: MXenes have a large specific surface area, which is commonly
measured in the hundreds to thousands of square metres per gramme. This large surface area
gives electrolyte ions plenty of room to adsorb, improving energy storage capacity.

Tunable Interlayer Spacing: By managing the etching process, the interlayer spacing of
MXenes can be changed. The integration of different electrolyte ions is made possible by
this tunability, increasing the overall capacitance and energy storage capacity of
supercapacitors.
In conclusion, the use of MXenes and MOFs in the electrode design of supercapacitors has
enormous promise for producing high-performance energy storage systems. MXenes and
MOFs open the door to the creation of new supercapacitors with increased energy and power
densities, longer cycle times, and higher overall performance thanks to their synergistic
effects, greater stability, variable pore diameters, and multifunctional electrode designs.

Doping (Preferably S-N ) :

To change a MOF's (Metal-Organic Framework) characteristics, additional atoms or

molecules are inserted into the MOF structure. Similar to semiconductor materials, doping is
a process where impurities are purposefully injected to influence conductivity or other
material properties.

-pg. 6
 7

Different techniques, such as post-synthetic doping or covalent modification during

synthesis, can be used to add doping to MOFs. The desired alteration of the MOF's
characteristics determines the dopant and doping technique to use.

Dopant – ThioUrea (S-N) :

In the experimental procedure, we took Metal Nitrate as the precursor material and ThioUrea
as the dopant (containing S-N atoms). Followed by Methanol as Solvent and 2-MIM
(MethylImidazole).

Adding thio urea to metal nitrate MOFs has a number of benefits and functionalization
possibilities. First off, the inclusion of sulfur atoms in thiourea molecules can add more
coordination sites for metal ions within the MOF framework, potentially improving the
structural stability and catalytic activity. Second, the distinct electronic and steric
characteristics of thio urea can have an impact on the MOF's physical characteristics,
including its porosity, surface area, and thermal stability. It is feasible to add additional
functionality and enhance the performance of MOFs in a number of applications by doping
them with thio urea.

Thiourea has been successfully incorporated into MOFs in recent studies, demonstrating the
economic potential of this doping technique. Thio urea-doped MOFs, for instance, have
demonstrated increased catalytic activity in a variety of activities, such as organic
transformations and gas adsorption procedures. Improved reaction speeds and selectivity can
result from the inclusion of thio urea moieties inside the MOF structure, which can enable
certain interactions with reactant molecules.

Thio urea doping additionally provides the chance to modify the MOF's electrical and steric
characteristics, affecting its porosity, surface area, and thermal stability. For applications like
gas adsorption and separation, where the addition of thio urea can improve the MOF's
capacity to selectively trap particular gases or molecules, these alterations can be extremely
important.

Numerous research have successfully incorporated thio urea into MOFs, demonstrating the
efficacy of this doping method. In comparison to undoped MOFs, thio urea-doped MOFs
-pg. 7
 8

have shown higher catalytic activity, increased gas adsorption capabilities, and changed
selectivity. These results show how thio urea doping can be used to modify the
characteristics of MOFs for use in catalysis, gas storage, sensing, and drug delivery.

4. LITERATURE WORK.

Nickel-MOF for Supercapacitors.

S.no Title of the article Synthesis Electrolyte Specific Energy Power

method used capacitance Density Density

1. Nickel metal–organic Solvother Potassium 742.2 F/g at 58.43 1,947 W/kg

framework (Ni-MOF) mal Hydroxide 1 A/g Wh/kg
derived NiO/C@CNF method (KOH)
composite for the
application of high
performance self-standing
supercapacitor electrode

2. Solvothermal synthesis of Solvother Potassium 1010 F/g at 20.2 250 W/kg

flower-string-like NiCo- mal Hydroxide 0.5 A/g Wh/kg
MOF/MWCNT composites method (KOH)
as a high-performance
supercapacitor electrode
material

3. Co-doped nickel sulfide Hydrother Potassium 332.8 mA 65.6 0.85

(NiS2) derived from mal Hydroxide h/g Wh/kg kW/kg
bimetallic MOF for high- method (KOH)
performance asymmetric
supercapacitors

4. Preparation of layered Solvother Potassium 1866 F/g at 57 775 W/kg

NiCo-MOF nanosheets for mal Hydroxide 1 A/g Wh/kg
high-performance method (KOH)
asymmetric supercapacitor
electrode material

5. Solvothermal synthesis of Solvother Potassium 850.42 F/g 18.66 1671 W/kg

binder free Ni-MOF thin mal Hydroxide Wh/kg
films for supercapacitor method (KOH)
electrodes

-pg. 8
 9

Mxenes induced Ni-MOF

S.No Title of the article Synthesis Electrolyte Specific Energy density Power
method used capacitance density

1. In situ synthesis In-situ Potassium 1160.5 F/g 48.2 Wh/kg 750 W/kg
of M (Fe, Cu, Co, synthesis hydroxide at 1 A/g
and Ni)- (KOH)
MOF@MXene
composites for
enhanced specific
capacitance and
cyclic stability in
supercapacitor
electrodes

2. Ni/Co- Hydrothermal Potassium 1924 F/g at 98.1 Wh/kg 600 W/kg

MOF@aminated Method hydroxide 0.5 A/g
MXene (KOH)
hierarchical
electrodes for
high-stability
supercapacitors

3. MXenes induced Hydrothermal Potassium 1124 Flg at 46 Wh/kg 800 W/kg

formation of Ni- Method hydroxide 1 A/g
MOF micro belts (KOH)
for high-
performance
supercapacitors

4. In Situ Growth of Hydrothermal Potassium 497.6 F/g at 223.9 Wh/kg 1953 W/kg
Ni-MOF Method hydroxide 0.5 A/g
Nanorods Array (KOH)
on Ti3C2Tx
Nanosheets for
super capacitive
Electrodes

5. Construction of Hydrothermal Potassium 186.3 F/g at 76.8 Wh/kg 860 W/kg

MOF-Derived Ni- Method hydroxide 1 A/g
Co-Se/MXene (KOH)
Heterostructured
Composite as
Hybrid
Supercapacitor
Cathode

-pg. 9
 10

Thio-Urea doped Nickel-MOF with Graphene for Supercapacitors.

S.no Title of the article Synthesis Electrolyte Dopant Specific

method used chemical capacitance

1. Ni-MOF derived Hydrother Potassium Thio- 649.22 C g− 1 at 3

NiO/Ni/r-GO mal Hydroxide Urea
nanocomposite as a method (KOH) A g− 1
novel electrode material
for high-performance
asymmetric
supercapacitor

2. Bifunctional rGO- Hydrother Potassium Thio- 972 F/g at 1A/g

NiCo2S4 MOF hybrid mal Hydroxide Urea
with high method (KOH)
electrochemical and
catalytic activity for
supercapacitor and
nitroarene reduction

3. Applications of metal- Hydrother Potassium Thio- 1325 F g-1

organic framework- mal Hydroxide Urea
derived N, P, S doped method (KOH)
materials in
electrochemical energy
conversion and storage

4. Metal-Organic Solvotherm DMF/water, Thio- 988 F g-1

Frameworks and Their al Potassium Urea
Derived method Hydroxide
FunctionalMaterials for (KOH)
Supercapacitor
Electrode Application

5. Facile synthesis of Hydrother Potassium Thio- 862.73 F g− 1

nanostructured sodium mal Hydroxide Urea
and MoS2 incorporated Approach (KOH)
Ni-MOFs with excellent
cyclic durability for
symmetric
supercapacitor
application

-pg. 10
 11

After analyzing the above-mentioned Research papers, it is noted that a minimal

amount of research is done in the field of development of Doped MOF-
Mxene/RGO composite materials for supercapacitor applications. The whole
area of interest of this research lies in the development of the above-mentioned
composite material which is to be used as material for the preparation of
electrodes in the supercapacitors. Furthermore, it has been decided to use the
Hydrothermal method in a High-pressure Autoclave to synthesize the MOF-
based Mxene/RGO.

Among various synthesis methods, the High-pressure autoclave

method is selected because this method facilitates the maximum extent of
diffusion of the reactants into the porous structure of MOF which in turn results
in the integration and uniform distribution of Mxene within the MOF matrix. It
also offers higher reaction control over conditions like temperature and
pressure. Reaction rates are also accelerated in this method resulting in higher
yields and purity of the product.

The reason for selecting Ni-based precursor material among the

various available precursor materials is that Ni+2 ions have an outer electronic
configuration of 3d8, these partially filled 3d electrons result in the pseudo
capacitor behavior of Ni-MOFs due to the participation in redox reactions. This
property of Ni also facilitates high electrical conductivity. A high degree of
chemical stability is also maintained which is crucial in the performance of
supercapacitors over various cycles.

-pg. 11
 12

5 MATERIALS AND METHODS

5.1 MATERIALS REQUIRED

Nickel nitrate hexahydrate (99%)
Graphene or MXene
Thiourea
Methanol
Methyl imidazole

5.2 EXPERIMENTAL PROCEDURE

5.2 a) Preparation of Nitrogen-doped Ni-MOF

Nitrogen-Doped Nickel was Synthesized by Hydrothermal

Method in a High-Pressure Autoclave. 6 g of NI(NO3)2⋅6H2O, and 0.78g
of Thiourea were dissolved in 100 MeOH (solution A), whereas 6.56 g of
2-MIM was dissolved in 100mL MeOH (solution B ). Subsequently, a
Mixture of solutions A and B was poured into the High-Pressure
Autoclave. Then, Nitrogen was Purged for 30min to create an inert
atmosphere in the chamber. The Experiment lasted for 4 hours at a
temperature of 120 degrees Celsius and a rotational frequency of 300 rpm
with Continuous Stirring.

5.2 b) Incorporating Mxene/Graphene

The autoclave solution was allowed to cool down to room

-pg. 12
 13

temperature. The reaction mixture which consists of solid components

suspended in the solvent is poured out of the auto-clave. This is introduced
to the Centrifuge. The reaction mixture is transferred into centrifuge bottles
and rotated at higher speeds in a centrifuge. The required product is
obtained after continuous washing with solvent(methyl alcohol). The final
solid product is introduced to a Vaccum Oven to remove residual solvent.
The dried powder is collected.
Different concentrations (0.5%, 1%, and 2%) of MXene/Graphene
and the nitrogen-doped Ni-MOF were dissolved in 100 milliliters of
MeOH. An ultrasonication session lasts for twenty minutes with this
solution ensuring that Mxene/Rgo sheets are evenly distributed in the
lattice of Nitrogen-doped Ni-MOF.

5.2 c) Cyclic voltammetry and Galavostatic Charge Discharge:

Procedure followed:

The composite MXene-MOF/RGO composite which was prepared

through synthesis, filtration, washing, and drying processes is blended
with a binder (such as PVDF) and a conductive additive (like carbon black)
in a solvent (such as NMP) to form a slurry. Apply this slurry onto a current
collector (for example, nickel foam or copper foil) and allow it to dry in a
vacuum oven. Subsequently, cut the coated current collector into the
desired electrode shapes.

In setting up the electrochemical testing, select a suitable electrolyte (e.g.,

1M KOH or 1M LiPF₆ in an organic solvent). Assemble a three-electrode
cell with the prepared electrode as the working electrode, a reference

-pg. 13
 14

electrode (e.g., Ag/AgCl ), and a counter electrode (e.g., platinum foil or

mesh). Fill the cell with the electrolyte solution. Alternatively, for a two-
electrode setup, use two identical electrodes and fill the cell with the
electrolyte.

When performing cyclic voltammetry (CV), connect the electrodes to a

potentiostat/galvanostat. Specify the scan rate (e.g., 5 to 100 mV/s),
potential range (e.g., -0.5 to 0.5 V vs. reference), and the number of cycles
(e.g., 10). Commence the CV experiment to apply a potential sweep and
measure the resulting current. Document the CV curves, which illustrate
the relationship between current and applied potential. Analyze the curves
to identify oxidation and reduction peaks and calculate specific capacitance
from the data.

For galvanostatic charge-discharge (GCD), link the two working electrodes

to the potentiostat/galvanostat. Set the current density (e.g., 1 to 10 A/g),
charge-discharge voltage window (e.g., 0 to 1 V), and the number of cycles
(e.g., 100). Execute the GCD experiment to apply a constant current and
measure the voltage changes during charging and discharging. Document
the GCD curves, which display voltage versus time.

Calculate specific capacitance using the formulae:

a) Using cyclic voltammetry:

The specific capacitance can be calculated as:

Cs = I.Δt /(m.ΔV)

where

-pg. 14
 15

I = Current at peak of CV curve

Δt = Time corresponding to the current
m = Mass of the active material
ΔV = Voltage difference

— Alternate formula using the area under the CV graph

Cs = A/(2mk.ΔV)
where A = Area under the CV graph
m=mass of the Active Material
k=Scan rate
ΔV = Voltage difference

b) Using Galvanostatic Charge Discharge(GCD):

Cs = I.Δt /(m.ΔV)
where
I = Discharge Current
Δt = Discharge time
m = Mass of the active material
ΔV = Voltage difference during discharge

6. RESULTS

Briefing on the techniques followed :

XRD(X-Ray Diffraction) :

A versatile scientific method for examining the arrangement of atoms or molecules in

crystalline materials is X-ray Diffraction (XRD). It offers insightful information on the
atomic composition, crystal structure, and characteristics of a wide range of substances,

-pg. 15
 16

from minerals and metals to organic molecules and complex materials. In domains
including materials science, solid-state physics, chemistry, geology, and others where
comprehending the arrangement of atoms is important, XRD is a vital tool.

The X-ray Diffraction Principle:

The basic idea behind X-ray diffractometry is based on how X-rays interact with the
regular arrangement of atoms in a crystal lattice. The atoms in the crystal lattice diffract or
scatter the X-rays when an X-ray beam is pointed at a crystalline sample. The effect of this
scattering is constructive interference, where the X-ray waves align and reinforce each
other, leading to the formation of a distinct diffraction pattern.

GCD :

Interpreting the Plot:

Potential Changes: Throughout the experiment, the plot depicts how the potential evolves.
Depending on how the experiment is set up, the potential may be increased or decreased,
maintained constant, or changed in a particular way.

Voltage Profile: The plot may show clearly defined plateaus or regions where the potential
is stable for a while before varying. These plateaus frequently coincide with particular
electrochemical processes like adsorption, desorption, or electrochemical reactions taking
place at the electrode interface.

Transient Periods: These times are when the potential is rapidly changing. The kinetics of
electrochemical processes, such as the charging or discharging of capacitive components,
can be learned from these transient periods.
For examining the behavior of the electrochemical system under particular
circumstances, these regions might be of interest. Sharp changes or peaks in the potential
can signify particular electrochemical events or reactions taking place in the system, like
the beginning of redox reactions or phase transitions.
-pg. 16
 17

Data analysis: To learn more about capacitance, faradaic reactions, electrode kinetics, and
other electrochemical parameters, researchers frequently use GCD plots. The potential
profile's slope or curve can reveal details about the system's behavior. Keep in mind that
the interpretation of the plot can change depending on the particular experimental design,
the kind of electrochemical system being studied, and the study's objectives.

3e ni (s-n) mof

-pg. 17
 18

3e ni(s-n) rgo 2%

-pg. 18
 19

co s-n mof

-pg. 19
 20

ni (s-n) mof n-autoclave

-pg. 20
 21

ni mof 1% mxene

-pg. 21
 22

ni mof rgo 1%

-pg. 22
 23

ni sn 0.5 % rgo

-pg. 23
 24

ni sn mxene .5 %

-pg. 24
 25

ni(s-n) 2% mxene

CV :

Interpreting the Plot:

Electrochemical reactions could take place during this scan and change the current.
Peak Characteristics: Different electrochemical processes are represented by peaks or
peaks and valleys in the current response. Species at the electrode surface may undergo
processes like oxidation (anodic peak) or reduction (cathodic peak).

Peak Potential: The term "peak potential" refers to the potential at which a peak occurs.
This can reveal details about the species' redox potential that are involved in
electrochemical reactions.
-pg. 25
 26

It has an impact on the CV plot's peak positions and shapes. Slower scan rates could
provide more information on intricate electrochemical processes.

Reverse Scan: The potential is frequently reversed after the forward scan is finished, and
this is when the "reverse scan" starts. The current varies as the potential returns to its initial
potential, as shown by the reverse scan. This gives us more details about how reversible
the electrochemical reactions are.

Faradaic and Non-Faradaic Processes: While non-Faradaic processes involve non-

electrochemical interactions, faradic processes involve the transfer of electrons between
species. Redox reactions are indicated by peaks that correspond to Faradaic processes.

Analysis: To learn more about the redox potentials, electron transfer kinetics, reaction
mechanisms, and electrochemical characteristics of the systems under study, researchers
analyze CV plots.
Always keep in mind that interpreting a CV plot can be challenging, particularly when
working with a variety of electrochemical reactions and experimental setups. For accurate
interpretation, knowledge of electrochemistry and the particular system under study is
essential.

-pg. 26
 27

3e ni (s-n) mof

-pg. 27
 28

3e ni(s-n) rgo 2%

-pg. 28
 29

co s-n mof

-pg. 29
 30

ni (s-n) mof n-autoclave

-pg. 30
 31

ni mof 1% mxene

-pg. 31
 32

ni mof rgo 1%

-pg. 32
 33

ni sn 0.5 % rgo

-pg. 33
 34

ni sn mxene .5 %

-pg. 34
 35

ni(s-n) 2% mxene

SAMPLE
CODE Area Scan Rate (mV/s) mass (g) V2-V1 Specific Capacitance (F/g)
Ni (s-n)
MOF 4.18E-04 5 0.0084 0.6 1.66E+01
Ni (s-n)
MOF 8.37E-04 10 0.0084 0.6 1.66E+01
Ni (s-n)
MOF 0.00113 20 0.0084 0.6 11.21031746
Ni (s-n)
MOF 1.30E-03 50 0.0084 0.6 5.16E+01
Ni (s-n)
MOF 0.00142 100 0.0084 0.6 2.817460317E+01

ni(s-n) rgo
2% 6.50E-04 5 0.0029 0.6 7.47E+01

co s-n mof 3.04E-03 5 0.0509 0.6 1.99E+01

-pg. 35
 36

co s-n mof 2.84E-03 10 0.0509 0.6 9.30E+00

co s-n mof 0.00426 20 0.0509 0.6 6.974459725
co s-n mof 0.00612 50 0.0509 0.6 4.007858546
co s-n mof 0.007 100 0.0509 0.6 2.292075966

Ni(s-n) 2%
mxene 1.37E-03 5 0.0013 0.6 2.2E+02
Ni(s-n) 2%
mxene 2.04E-03 10 0.0013 0.6 1.90E+02
Ni(s-n) 2%
mxene 0.0025 20 0.0013 0.6 160.2564103
Ni(s-n) 2%
mxene 0.00292 50 0.0013 0.6 74.87179487
Ni(s-n) 2%
mxene 0.00314 100 0.0013 0.6 40.25641026

ni sn
mxene .5
% 7.20E-04 5 0.0561 0.6 4.28E+01
ni sn
mxene .5
% 9.40E-04 10 0.0561 0.6 2.79E+01
ni sn
mxene .5
% 0.00114 20 0.0561 0.6 1.693404635
ni sn
mxene .5
% 0.00135 50 0.0561 0.6 0.8021390374
ni sn
mxene .5
% 0.0015 100 0.0561 0.6 0.4456327986

ni sn 0.5 %
rgo 4.64E-04 5 0.0432 0.6 3.58E+01
ni sn 0.5 %
rgo 4.58E-04 10 0.0432 0.6 1.77E+01
ni sn 0.5 %
rgo 5.28E-04 20 0.0432 0.6 1.02E+00
ni sn 0.5 %
rgo 7.85E-04 50 0.0432 0.6 6.06E-01
ni sn 0.5 %
rgo 0.00111 100 0.0432 0.6 0.4282407407

Ni MOF
Rgo 1% 1.20E-03 5 0.0446 0.6 8.97E+01
Ni MOF 7.55E-04 10 0.0446 0.6 2.82E+01

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Rgo 1%
Ni MOF
Rgo 1% 8.39E-04 20 0.0446 0.6 1.57E+01
Ni MOF
Rgo 1% 1.17E-03 50 0.0446 0.6 8.74E-01
Ni MOF
Rgo 1% 0.00159 100 0.0446 0.6 0.5941704036

Ni MOF 1%
mxene 4.44E-04 5 0.048 0.6 7.08E+01
Ni MOF 1%
mxene 5.47E-04 10 0.048 0.6 5.90E+01
Ni MOF 1%
mxene 6.85E-04 20 0.048 0.6 4.19E+01
Ni MOF 1%
mxene 9.03E-04 50 0.048 0.6 1.27E+01
Ni MOF 1%
mxene 0.0011 100 0.048 0.6 0.3819444444

XRD Analysis :

X-ray diffraction (XRD) is a flexible scientific technique that can be used to investigate the
configuration of atoms or molecules in crystalline materials. It provides insightful details
about the properties, atomic makeup, and crystal structure of a broad variety of materials,
including organic molecules, complex materials, minerals, and metals. X-ray diffraction
(XRD) is an essential technique in many fields, such as materials science, solid-state
physics, chemistry, geology, and others where understanding atom arrangement is crucial.

X-ray diffractometry's fundamental principle is based on how X-rays interact with atoms
arranged in a crystal lattice. When an X-ray beam is directed towards a crystalline sample,
the atoms in the crystal lattice diffract or scatter the X-rays. A characteristic diffraction
pattern is formed as a result of the X-ray waves aligning and reinforcing one another
through the process of constructive interference.

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Sample Notations :

1.Nickel Nitrate – Thio-Urea, RGO 0.5%

2. Nickel Nitrate – Thio-Urea, RGO 1%

3. Nickel Nitrate – Thio-Urea, Mxene 0.5%

4. Nickel Nitrate – Thio-Urea, Mxene 1%

5. Nickel Nitrate – Na-Se MOF

Sample 1 : Nickel Nitrate – Thio-Urea, RGO 0.5%

In the given sample, we observe that thio-urea(N-doping) has been doped to nickel
nitrate(precursor) and was composited with 0.5% of RGO(reduced graphene oxide).And,
from the XRD-plot we notice a large sharp peak at an angle of 11 degrees(2theta) and a
few sharp peaks at 16 degrees, 22 degrees and 26 degrees. From the research articles we
have gone through, we observed nitrogen doped Ni-MOFs at angles 20-25 degrees.

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From the XRD-plot, we were able to match the peaks with the standard data from the
articles and ensure the presence of nitrogen doped Ni-MOF.

Then, we also observe peaks at 26 degrees and 37 degrees which shows the presence of
RGO. It matches with the peaks that are evident from the research articles where RGO
peaks form between 24-26 degrees.

Sample 2 : Nickel Nitrate – Thio-Urea, RGO 1%

Similarly, the XRD-plot of this sample shows small yet broad peaks at around 11 degrees
and 30 degrees. Which is more or less the same as sample 1. But, we can observe a slight
shift in the peak positions towards the right, this scenario is due to the presence of more
free electrons which increases the angle of diffraction.

So, we can ensure the presence of N-doped Ni-MOF and RGO from the above peaks of the
XRD-plot.

Sample 3 : Nickel Nitrate – Thio-Urea, Mxene 0.5%

In this sample, though the precursor material and dopant remain same i.e., Nickel Nitrate
and Thio-urea, we dissolved 0.5% of Mxene in it, so as to form a composite material.

From the plot, we observe small and sharp peak at around 13 degrees, which ensures us the
presence of N-doped Ni-MOF

Then, we observe a few more peaks at 21 degrees, 26 degrees and 33 degrees. From the
articles we have gone through, we noticed doped MOF with Mxene as a composite showed
peaks on XRD-plot between 20-40 degrees.So, we were able to match with the standard
peaks and conclude the presence of N-doped Ni-MOF and Mxene in the given sample.

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Sample 4 : Nickel Nitrate – Thio-Urea, Mxene 1%

Following the trend, the XRD-plot of the sample gave us peaks at around 11 degrees, 31
degrees.

The first peak at 11 degrees corresponds to the presence of N-doped Ni-MOF, whereas the
second peak at 31 degrees shows us the presence of Mxene in the sample.

Also, we noticed that, with increase in the concentration of Mxene, the position of the
peaks shifted slightly towards right, indicating that the presence of more free electrons thus
resulting in more angular diffraction.

Sample 5: Nickel Nitrate – Na-Se MOF

In the given sample, we maintained the precursor material as Nickel Nitrate, but the dopant
was changed to Sodium Selenium(Na-Se).

From the XRD-plot, we notice small peaks at around 13 degrees and 27 degrees.

Upon studying various research papers, we came to know that, the sodium selenium doped
Ni-MOFs showed peaks on the XRD between 25-45 degrees.The first peak formed in low
angle region ensures the presence of Ni-MOF, whereas the second peak formed at 27
degrees ensures the presence of sodium selenium(Na-Se) in the given sample.

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ANALYSIS ON THE VALUES OF SPECIFIC CAPACITANCE

By following the experimental procedure mentioned above,different MOFs were

additionally changed to Mxene-MOF composites.Then, Cyclic voltammetry (CV) and
Galvanostatic Charge Discharge(GCD) tests were conducted on these samples.The tests
were conducted on Ni thiourea MOF substance with varying MXene composition namely
0.5,1,2% and also with varying RGO composition namely 0.5,1,2%.

From the results obtained from the above-mentioned tests, it can be stated
that different values of the specific capacitance were obtained for the same sample if the
Scan rate(mV/s) is changed from 5 to 100mV/s.The main aim of conducting these tests is
to figure out the scan rate at which we could get the maximum specific capacitance
value.In that aspect,the following are the conclusions made for each of the sample taken:

Ni(SN) MOF at the scan rate of 5 and 10mV/s has a specific capacitance
value of 16.6F/g.Next,Co thiourea MOF at the scan rate of 5mV/s has a specific
capacitance value of 19.9F/g. Similar to the other samples, Ni thiourea 0.5% mxene has
42.9F/g at the scan rate of 5mV/s.Ni thiourea with 1% mxene has 70.8F/g at the scan rate
of 5mV/s.Ni thiourea.2% mxene Ni thiourea mof had a value of specific capacitance
220F/g at the scan rate of 5mV/s .Similarly with RGO MOF composites .

The specific capacitance for Ni thiourea MOF with RGO 0.5% at the scan
rate of 5mV/s is 35.8 F/g And for Ni thiourea with RGO 1% is 89F/g at the scan rate of
5mV/s.Finally, the scan rate of Ni thiourea with 2% RGO for which the maximum value of
the specific capacitance is recorded is 74.7F/g at 5mV/s.

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It is observed that there is an inverse relationship between the specific

capacitance and various scan rates used in the process of cyclic voltammetry. As the scan
rates increased there was a decrement in the values of the specific capacitance. This can be
attributed to the fact that at low scan rates, there is sufficient time for the electrolyte ions to
diffuse into the porous structure of the electrode material, allowing the full utilization of
the active material for charge storage. This leads to a higher measured specific capacitance.
At high scan rates, the time for ion diffusion is limited. Only the outer surface of the
electrode material may be accessible for charge storage, leading to lower utilization of the
active material and, consequently, a lower specific capacitance.

Based on the results, based on the value of maximum specific capacitance

value, and also by taking various other factors into consideration, the best suitable material
could be selected for the application of synthesizing the supercapacitor.

7. CONCLUSION:
In this process of developing a suitable material for synthesizing the electrode
material for supercapacitors, various research papers were referred and the most suitable
precursor materials and the suitable dopants were selected for the desired result. the Ni
MOF is selected and it is incorporated with the Mxene and RGO materials with various
compositions namely 0.5%,1%, and 2% respectively. So finally after undergoing various
papers, the synthesizing method was selected and the doping material was selected as the
thiourea. Then the characterization techniques namely XRD, CV, and GCD were
conducted on these samples, and the final outputs from the tests were noted down for the
desired selection of material for supercapacitor applications from the observations we
received from the outputs of the tests, it can be concluded that Ni thiourea MOF with 2%
Mxene has a specific capacitance of 220F/g which is quite useful in supercapacitor
applications.So from our observations and this part of research, we can suggest that this
material can be selected as the electrode material for supercapacitor applications.
But we cannot come to the final understanding that this material can be selected

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as the material for supercapacitor applications directly with these results. More research
has to be done on the synthesized materials other than the ones which were did in this work
to come to the final conclusions. Some other tests like scanning electron microscopy
(SEM) transmission electron microscopy(TEM), cyclic stability tests and similar tests
need to be done for the final output in this regard.

8. REFERENCES :

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