Synthesis and characterization of Graphene by Electrochemical Process

CHAPTER 1

INTRODUCTION

1.1 Graphene

It is an allotrope of carbon consisting of a single layer of atoms arranged

in two-dimensional honeycomb lattice. The name is a portmanteau of “graphite” and the
suffix -ene, reflecting the fact that the graphite allotrope of carbon consists of stacked
graphene layers.

Each atom in a graphene sheet is connected to its three nearest neighbours by

a σ-bond, and contributes one electron to a conduction band that extends over the whole
sheet. This is the same type bonding seen in carbon nanotubes and polycyclic aromatic
hydrocarbons, and (partially) in fullerenes and glassy carbon. These conduction bands
make graphene a semimetal with unusual electronic properties that are best described by
theories for mass less relativistic particles. Charge carriers in graphene show linear, rather
than quadratic, dependence of energy on momentum, and field-effect transistors with
graphene can be made that show bipolar conduction. Charge transport is ballistic over long
distances; the material exhibits large quantum oscillations and large and
nonlinear diamagnetism. Graphene conducts heat and electricity very efficiently along its
plane. The material strongly absorbs light of all visible wavelengths, which accounts for
the black colour of graphite; yet a single graphene sheet is nearly transparent because of its
extreme thinness. The material is also about 100 times stronger than would be the strongest
steel of the same thickness.

Scientists have theorized about graphene for decades. It has likely been
unknowingly produced in small quantities for centuries, through the use of pencils and
other similar applications of graphite. It was originally observed in electron microscopes in
1962, but only studied while supported on metal surfaces. The material was later

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rediscovered, isolated and characterized in 2004 by Andre Geim[1] and Konstantin

Novoselov[1] at the University of Manchester, who were awarded the Nobel Prize in
Physics in 2010 for their research on the material. High-quality graphene proved to be
surprisingly easy to isolate.

The global market for graphene was $9 million in 2012, with most of the demand
from research and development in semiconductor, electronics, electric
batteries, and composites. In 2019, it was predicted to reach over $150 million by 2021.

The IUPAC recommends use of the name “graphite” for the three-dimensional
material, and “graphene” only when the reactions, structural relations or other properties of
individual layers are discussed. A narrower definition, of “isolated or free-standing
graphene” requires that the layer be sufficiently isolated from its environment, but would
include layers suspended or transferred to silicon dioxide or silicon carbide.

History of Graphene

A discussion of the history of graphene would be incomplete without a brief

mention of graphite oxide (GO), graphene oxide (i.e., exfoliated GO), and graphite
intercalation compounds (GICs), as currently graphene and a related material called
“reduced graphene oxide (r-GO)” (see below) are frequently prepared by the manipulation
of GO and graphene oxide, which, remarkably, have been studied extensively for more
than 170 years. The earliest reports of GO and GICs can be traced back to the 1840s, when
the German scientist Schafhaeutl reported the intercalation (that is, insertion of a
small-molecule species, such as an acid or alkali metal, in between the carbon lamellae)
and exfoliation of graphite with sulfuric and nitric acids. A wide range of intercalants and
exfoliants have been used since that time, including potassium (as well as other alkali
metals), fluoride salts of various types, transition metals (iron, nickel, and many others),
and various organic species. The stacked structure of graphite is retained in GICs, but the
interlayer spacing is widened, often by several angstroms or more, which results in
electronic decoupling of the individual layers. This electronic decoupling leads, in some

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cases, to intriguing superconductivity effects: a harbinger of the extraordinary electronic

properties later demonstrated in freestanding graphene. In fact, the term “graphene” grew
out of the chemistry of GICs as the need for language to describe the decoupled layers
became apparent. (To the best of our knowledge, the term graphene was first coined by
Boehm et al. in 1986). It was later reasoned that if the interlayer spacing of GICs could be
extended throughout the entire structure, and the small molecule spacers removed, pristine
graphene may be obtained.

In 1859 Benjamin Brodie noted of the highly lamellar structure of thermally

reduced graphite oxide. In 1916, Peter Debije and P. Scherrer determined the structure of
graphite by powder X-ray diffraction. The structure was studied in more detail by V.
Kohlschütter and P. Haenni in 1918, who also described the properties of graphite oxide
paper. Its structure was determined from single-crystal diffraction in 1924.

The theory of graphene was first explored by P. R. Wallace in 1947 as a starting

point for understanding the electronic properties of 3D graphite. The emergent massless
Dirac equation was first pointed out in 1984 by Gordon Walter Semenoff,David P.
DiVincenzo, and Eugene J. Mele.Semenoff emphasized the occurrence in a magnetic field
of an electronic Landau level precisely at the Dirac point. This level is responsible for the
anomalous integer quantum Hall effect.

Fig. 1.1 Timeline of selected events in the history of the preparation, isolation, and
characterization of graphene.

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1.2 Graphene Synthesis Methods

As already mentioned, that graphene is found to be intelligent material for many

advanced industrial purposes despite its excellent properties. Since graphene was
discovered, industrialists have been finding suitable fabrication methods for producing
high quality, defect free, stable and high yield and cost-effective methodologies.
Fabrication methodology of graphene is challenging task, because utilization this material
for different applications mostly depends on fabrication methods at large scale.

1.2.1 Micromechanical exfoliation

Micromechanical exfoliation is method of producing graphene-based materials

which involves peeling systematically ordered pyrolytic graphite with the use of adhesive
tape. It is a methodology of production of graphene, during this process graphene is
separated from graphite crystals Peeling is the method used to produce graphene by peeling
it off the graphite. After completion of the peeling, multilayer graphene’s are remains on
the tape. Graphene is sliced into various flakes of few layers by continuously peeling the
multi-layer graphene. In this process layers of graphene are bonded strongly by van der
Waals bonding. Schematic diagram of micromechanical exfoliation. It is simple easy
manufacturing method for producing graphene materials but, it is not suitable for large
scale growth of graphene materials. Information related to production procedure to make
graphene can available in literature.

1.2.2 Liquid-phase exfoliation (LPE)

Liquid phase exfoliation is method of production of graphene materials by using

solvent like acetic acid, sulphuric acid and hydrogen peroxide, to exfoliate graphite
through ultrasonication. Sonication methodology is used in LPE to exfoliate the graphene
from graphite material, as graphite contains different layers of graphene which attached by
Van der Waals forces. This method used to create graphene nanoribbons, but large-scale
growth of graphene is difficult task in this method also. Details of LPE to produce
graphene can get from literature.

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1.2.3 Chemical vapor deposition (CVD)

CVD is one of the important deposition methodologies used to transition metals. In

CVD process, nickel and copper used for large scale production of graphene. During CVD
process, film of metallic catalyst deposits on the substrate. Chemical etching is performed
on the deposited material on the substrate. After chemical etching, a mixture which
containing the carbon is passed into the reaction chamber. Experimental set up of CVD
process. The quality of the graphene obtained from CVD process is high quality. More
information regarding to CVD can be available in literature.

1.2.4 Flame synthesis

Flame synthesis is widely used mass production method for making nano particles.
This method is not well adopted for production of graphene as compared to chemical vapor
deposition. Some researchers have focused to use of flame synthesis for making graphene
materials due to its advantages like scalability and cost effectiveness. Experimental
procedure of flame synthesis. Some researchers suggested that flame synthesis has
potential to produce graphene economically.

1.2.5 Pulsed laser deposition (PLD)

PLD is a widely used method of growth approach for producing almost all types of
materials. During PLD process, laser energy source is outside the chamber; and chamber is
maintained ultrahigh vacuum. Schematic diagram of PLD is given in Figure 9. In this
process, material is deposited by at an angle of 45° by stoichiometry transfer between
ablated target and substrate material. During this process, substrates are added to its
surfaces parallel to the target at distance of 2–10 mm. Main advantages of PLD process is
low temperature growth rate achieved such that high-quality graphene made without
defects. Reader can get more details related PLD in literature.

1.2.6 Hummers Method

In this method powdered flake of graphite is mixed with NaNo3 and H2SO4. Next
KMnO4 is added slowly by maintaining the required temperature. The temperature of the
mixture is maintained below 5° C. The suspension is then reacted in an ice bath and stirred

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before again stirred in a 40° C water bath. The temperature of the mixture is constantly
maintained while water is added continuously. Also, DI water is used for frequent
treatments. In this method basically, graphite is converted into graphene oxide first and
then into graphene. There are several modifications experimented on basic hummers
approach in order to achieve modified graphene. However, assist is found that all the
approaches are similar to the fundamental approach of producing graphene using hummers
method. Some involve more chemicals and some use them at a later stage.

1.3 Microstructural characterization

Structure of Graphene

Bonding:

Carbon orbitals 2s, 2px, 2py form the hybrid orbital sp2 with three major lobes at 120°. The
remaining orbital, pz, is sticking out of the graphene’s plane.

Sigma and pi bonds in graphene. Sigma bonds result from an overlap of sp2 hybrid orbitals,
whereas pi bonds emerge from tunnelling between the protruding pz orbitals.

Three of the four outer-shell electrons of each atom in a graphene sheet occupy
three sp2 hybrid orbitals – a combination of orbitals s, px and py — tha are shared with the

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three nearest atoms, forming σ-bonds. The length of these bonds is about
0.142 nanometres.

The remaining outer-shell electron occupies a pz orbital that is oriented

perpendicularly to the plane. These orbitals hybridize together to form two
half-filled bands of free-moving electrons, π and π∗, which are responsible for most of
graphene’s notable electronic properties. Recent quantitative estimates of aromatic
stabilization and limiting size derived from the enthalpies of hydrogenation (ΔHhydro) agree
well with the literature reports. Graphene sheets stack to form graphite with an interplanar
spacing of 0.335 nm (3.35 Å). Graphene sheets in solid form usually show evidence in
diffraction for graphite’s (002) layering. This is true of some single-walled
nanostructures. However, unlayered graphene with only (hk0) rings has been found in the
core of premolar graphite onions. TEM studies show faceting at defects in flat graphene
sheets and suggest a role for two-dimensional crystallization from a melt.

SEM (Scanning Electron Microscope):

In 1931 Max Knoll and Ernst Ruska at the university of Berlin built the first
electron microscope that use accelerated electrons as a source instead of light source.
However, the first scanning electron microscope (SEM) was built in 1938 due to the
difficulties of scanning the electrons through the sample. Electron microscope is working
exactly the same as the optical microscope expects it use a focused accelerated electron
beam. Since the invention of the electron microscope, it became one of the most useful
instruments that has an impact in understanding scientific phenomena in different fields,
such as physics, nanotechnology, medicine, chemistry biology,etc. Electron microscope
has the ability to resolve objects ranging from part of Nano-metre to micro-metre
compared to light microscope that has a magnification in the range of 1000 and resolution
of 200 nm. In the first part of the chapter, we will describe some of the basics of electronic
microscope and its applications. The second part will be dedicated to the results obtained
mainly by SEM.

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Fig. 1.1 Scanning Electron Microscope Device Fig. 1.2 SEM image

XRD (X-Ray Diffraction):

X-ray diffraction (XRD) is a powerful non-destructive technique for characterizing

crystalline materials. It provides information on structures, phases, preferred crystal
orientations (texture), and other structural parameters, such as average grain size,
crystallinity, strain, and crystal defects. X-ray diffraction peaks are produced by
constructive interference of a monochromatic beam of X-rays scattered at specific angles
from each set of lattice planes in a sample. The peak intensities are determined by the
distribution of atoms within the lattice. Consequently, the X-ray diffraction pattern is the
fingerprint of periodic atomic arrangements in a given material. This review summarizes
the scientific trends associated with the rapid development of the technique of X-ray
diffraction over the past five years pertaining to the field of pharmaceutical industry,
forensic science, geological applications, microelectronics and glass industry, as well as in
corrosion analysis.

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Fig. 1.3XRD Device Fig. 1.4 XRD Image

EDAX (Energy Dispersive X-ray Analysis):

EDAX Analysis stands for Energy Dispersive X-ray analysis. It is sometimes
referred to also as EDS or EDAX analysis. It is a technique used for identifying the
elemental composition of the specimen, or an area of interest thereof. The EDX analysis
system works as an integrated feature of a Scanning Electron Microscope (SEM), and
cannot operate on its own without the latter.

During EDX Analysis, the specimen is bombarded with an electron beam inside the
scanning electron microscope. The bombarding electrons collide with the specimen atoms’
own electrons, knocking some of them off in the process. A position vacated by an ejected
inner shell electron is eventually occupied by a higher-energy electron from an outer shell.
To be able to do so, however, the transferring outer electron must give up some of its
energy by emitting an X-ray.

The amount of energy released by the transferring electron depends on which shell
it is transferring from, as well as which shell it is transferring to. Furthermore, the atom of
every element releases X-rays with unique amounts of energy during the transferring
process. Thus, by measuring the amounts of energy present in the X-rays being released by

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a specimen during electron beam bombardment, the identity of the atom from which the
X-ray was emitted can be established.

The output of an EDX analysis is an EDX spectrum. The EDX spectrum is just a
plot of how frequently an X-ray is received for each energy level. An EDX spectrum
normally displays peaks corresponding to the energy levels for which the most X-rays had
been received. Each of these peaks are unique to an atom, and therefore corresponds to a
single element. The higher a peak in a spectrum, the more concentrated the element is in
the specimen.

Fig.1.5EDAX Device Fig. 1.6 EDAX Image

1.4 Applications of graphene

Graphene is intelligent material which exhibits excellent properties used for
various industrial applications. Some of the notable applications where grapheme started
using to create the parts are given as follows.

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1.4.1 Graphene in high speed electronics

One can found the importance of electronics in most of the industrial applications
from medical to mechanical to optical to energy. Conductivity property of electronics need
to high for making electronics devices efficient and effective for usage in real world
applications. Graphene is one of the advanced materials that exhibits high conductivity
which considered as ideal for high speed electronics. However, commercial applications of
graphene have in initial stages only. Graphene is zero band gap material, more studies
needed for of usage industrial applications. Research groups indicating that graphene field
is advancing fast to create high speed graphene transistors for applying consumer
electronic devices very soon.

1.4.2 Graphene in data storage

Data storage is one of the important areas of research. Investigators are developing
the powerful small size hard drives to store higher capacity of data. Researchers suggested
that replacing indium tin oxide electrodes with polymers and grapheme oxide exhibit
write-read-read-rewrite features. Graphene based storage devices are10 times more
powerful than the currently available storage drives. Making small size storage devices is
not an issue but increasing capacity levels of storage devices is much importance task.
With applications of graphene oxide devices will create big difference in modern industrial
environments.

1.4.3 Graphene in LCD smart windows and OLED displays

Liquid crystal display (LCD) smart window is flexible device which consist of a
layer of liquid crystals sandwiched between two flexible electrodes made of flexible
polymer and graphene. Organic light emitting diode (OLED) windows are also utilized
graphene-based OLED counter electrodes. Currently LCDs and OLED technologies utilize
indium tin oxide counter electrodes. These materials are brittle in nature and limited
availability in the world. Compared to indium tin oxide, graphene is flexible and
availability is more/limitless. Usage of graphene in producing flexible smart devices like
mobiles and tablet devices is an important research area due to its excellent properties.

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1.4.4 Graphene in super capacitors

Present days electronics are occupying almost every industrial application.Energy

storage devices are highly required in every electronics to delivering high electric currents
within short time. Super capacitor is one of the important energy storage devices which
utilizes high internal surface area to store charge to delivers higher currents compared to
normal capacitors. Graphene can be highly suitable for making super capacitors due to its
higher internal area property. More research attempts are performing to create
graphene-based super capacitors for many advanced applications.

1.4.5 Graphene in solar cells/photovoltaic cell

Solar energy is one of the alternatives, and usage is increasing due to shortage of
fusil fuels. Solar cell is important element in solar device which plays critical role to absorb
energy from sun light. Presently, platinum-based electronics are using to produce solar
cells or photovoltaic cells. Due to higher cost of platinum based solar cells limits its usage
in industries. On the other hand, graphene is excellent conductor which is potential
material for solar cells. Graphene based electrodes can be made low cost as well as weight
while maintaining the efficiency.

1.4.6 Graphene in thermoelectric applications

Thermoelectric materials (TEM) are useful to convert thermal energy to electrical

energy and vice versa. TEM are highly used in Peltier coolers and thermoelectric power
generators. Graphene materials exhibits excellent thermoelectric properties which
triggering industrialists to make attention to use graphene in thermoelectric applications.

1.4.7 Graphene in shape memory materials

Shape memory polymers (SMP) are smart materials which have wide range of
industrial applications from biomedical to space applications. Graphene is better
alternative as shape memory material due to its shape memory, thermal and mechanical
properties as compared to existing SMP material namely polyurethane.

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1.4.8 Graphene in self-healing materials

Material properties like long term stability and durability are much needed for
structural and coating applications. Presently, polymeric composites are using said purpose
and efficiency of these materials depends on many interacting parameters such as
environmental condition, erosion, corrosion, etc. Self-healing of material indicates that
material should heal basically mechanical properties when material gets damaged.
Graphene is found to be potential material among the other materials like polymer
composites, metals, ceramics and its related alloys, due to shape memory effect and
self-healing ability.

1.4.9 Multifunctional graphene nanocomposite foams for space applications

Space and aerospace are highly advanced industries need intelligent materials
which combine functionalities with low weight, minimized volume and cost effectiveness.
Weight and volume of material used for space application are significantly influences cost
of the satellite/space vehicles. Joule heating property of metallic parts requires additional
cooling devices which adds weight and cost. Graphene is found to be better alternative
material for space applications due to its superior electronic and thermal properties. With
us of graphene as material for space applications, weight, volume and cost can be
optimized and Joule heating can also be suppressing due ballistic electron transport
property of graphene.

1.4.10 Graphene in electrorheology materials

Electrorheology (ER) materials are important smart material where rheological

properties of material like viscosity, shear stress and dynamic modulus, can bereversibly
transformed by the application of external electric field. ER materials M are widely using
for producing damper systems, ER polishing, tactile displays,medical devices, robotic
actuators, etc. Graphene is one material which is well suited additive for ER material due to
its unique properties.

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1.4.11 Other applications

As mentioned earlier that usage and growth of graphene and related materials are
increasing enormously in advanced applications like gene delivery and bio imaging, tissue
engineering, graphene based metal air batteries, graphene LED bulbs, graphene antennas,
graphene functional inks, graphene based fabric, etc.

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CHAPTER 2

LITERATURE REVIEW
2.1 Graphene

D.V.Lohar

Graphene is the thinnest material known to man at one atom thick, and also incredibly
strong - about 200 times stronger than steel. On top of that, graphene is an excellent
conductor of heat and electricity and has interesting light absorption abilities. It is truly a
material that could change the world, with unlimited potential for integration in almost any
industry. Graphene can also be added to metals, polymers and ceramics to create
composites that are conductive and resistant to heat and pressure. Graphene composites
have many potential applications, with much research going on to create unique and
innovative materials. The potential of graphene composites includes medical implants,
engineering materials for aerospace and renewables and much more. In this paper literature
review is done to know various techniques to produce grapheme composites and its
properties for various applications [2].

Graphene is a one-atom-thick layer of carbon atoms arranged in a hexagonal lattice.

It is the building-block of Graphite (which is used, among others things, in pencil tips), but
graphene is a remarkable substance on its own - with a multitude of astonishing properties
which repeatedly earn it the title “wonder material”. Graphene is the thinnest material
known to man at one atom thick, and also incredibly strong - about 200 times stronger than
steel. On top of that, graphene is an excellent conductor of heat and electricity and has
interesting light absorption abilities. It is truly a material that could change the world, with
unlimited potential for integration in almost any industry. Graphene is an extremely
diverse material and can be combined with other elements (including gases and metals) to
produce different materials with various superior properties. Researchers all over the world
continue to constantly investigate and patent graphene to learn its various properties and
possible applications. Composite materials (also referred to as composition materials, or

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simply composites) are materials formed by combining two or more materials with
different properties to produce an end material with unique characteristics. These materials
do not blend or dissolve together but remain distinct within the final composite structure.
Composite materials can be made to be stronger, lighter or more durable than traditional
materials due to properties they gain from combining their different components.

2.1.1Hummers method

N.I. Zaabaa , K.L. Fooa, U. Hashima, S.J.Tanb,c, Wei-Wen Liua , C.H. Voona

As an important precursor and derivate of graphene, graphene oxide (GO) has

received wide attention in recent years. However, the synthesis of GO in an economical
and efficient way remains a great challenge. Here we reported an improved NaNO3-free
Hummers method by partly replacing KMnO4 with K2FeO4 and controlling the amount of
concentrated sulfuric acid. As compared to the existing NaNO3-free Hummers methods,
this improved routine greatly reduces the reactant consumption while keeps a high yield.
The obtained GO was characterized by various techniques, and its derived graphene
aerogel was demonstrated as high-performance supercapacitor electrodes. This improved
synthesis shows good prospects for scalable production and applications of GO and its
derivatives. Graphene, a single layer of carbon atoms bonded into a honeycomb
two-dimensional lattice, has attracted great interests from scientists and engineers because
of its extraordinary properties and wide applications2,3, such as functional films, electric
devices and energy storage devices (Li-ion batteries, supercapacitors) etc. Different from
graphene, which is almost not soluble and cannot be dispersed in water or any organic
solvent, graphene oxide (GO) contains high-density oxygen functional groups, like
hydroxyl and epoxy group on its basal plane, and carboxyl at its edge4,5. They afford GO
with excellent water solubility, ease of functionalization and convenience in processing
etc.6,8, making it the most popular precursor of graphene. Undoubtedly, it is of great
significance to develop economical, eco-friendly and scalable routines to produce GO [3].

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Experimental procedure

Preparation of graphene oxide by a modified hummer’s method in typical

procedure, graphene oxide (GO) was produced using modified hummers method from pure
graphite powder. In this method, 27 ml of sulphuric acid (H2SO4) and 3 ml of phosphoric
acid (H3PO4) (volume ratio 9:1) were mixed and stirred for several minutes. Then 0.225 g
of graphite powder was added into mixing solution under stirring condition. 1.32 g of
potassium permanganate (KMnO4) was then added slowly into the solution. This mixture
was stirred for 6 hours until the solution became dark green. To eliminate excess of
KMnO4, 0.675 ml of hydrogen peroxide (H2O2) was dropped slowly and stirred for 10
minutes. The exothermic reaction occurred and let it to cool down. 10 ml of hydrochloric
acid (HCl) and 30ml of deionized water (DIW) was added and centrifuged using
Eppendorf Centrifuge 5430R at 5000 rpm for 7 minutes. Then, the supernatant was
decanted away and the residuals was then rewashed again with HCl and DIW for 3 times.
The washed GO solution was dried using oven at 90 °C for 24 hours to produce the powder
of GO. 2.2 Preparation of graphene oxide solution To produce acetone graphene oxide
(A-GO) and ethanol graphene oxide (E-GO) samples,1 mg of GO were dissolve in 1 ml of
acetone/ethanol solution (volume ratio 1:1) under ultrasonic for 1 hour. 100 µl of
A-GO/E-GO solution were then dropped on silicon wafer and spin at 2000 rpm for 20
second. The coated sample were then heated on the hot-plate with 80 °C for 10 minutes.
This step was repeated for 10 times. Same coating process was done on interdigitated
electrode (IDE) sample, which was mainly for electrical properties study.

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Fig. 2.1 Schematic illustration of IDE functional by GO

We applied improved hummer’s method in our experiment as to produce graphene

oxide, and different from conventional hummer method because synthesis graphene oxide
without using NaNO3. It shows that, NaNO3 does not affect the synthesis method to
produce graphene oxide. Without using NaNO3 still produce same characteristic of GO.
This method can decrease coast and free toxic gases. Ethanol and acetone used to perform
liquid medium of GO. Ethanol and acetone slightly affect the result of the synthesis of GO.
Ethanol has advantages more than acetone in form of conductivity of electrical and
solubility of GO. Conductivity of sample effected through morphology of GO. These
finding is confirmed by the SEM, XRD result, FTIR spectre and I-V curves. Morphology
of E-GO structure appeared in large agglomerates but A-GO seemed to be scattered on
silicon wafer. E-GO has higher current flow than A-GO because of the contact between the
flakes GO as shown at SEM. In FTIR spectre both sample contain several functional
groups such as hydroxyl, epoxy, carboxyl and carbonyl. Besides that, due to the lower
diffraction peak of A-GO, XRD result shows the interlayer spacing of A-GO sample is
slightly higher than EGO sample.

Ji Chen, Bowen Yao, Chun Li, Gaoquan Shi

Graphene has a unique atom-thick two-dimensional structure, excellent electronic,

mechanical, optical and thermal properties. Therefore, it has been widely explored for the
applications in electronics, catalysis, sensors, and energy conversion and storage, etc. For

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these purposes, the mass-production of graphene materials at low costs is one of the
essential requirements. Actually, graphene sheets already exist in nature and we need to
exfoliate them from their precursors. The exfoliation of graphite to graphene can be
realized either physically or chemically. Among the various methods, chemical reduction
of graphene oxide (GO) to reduced graphene oxide (rGO) is unique and attractive because
of its capability of producing single-layer graphene in large scale and at relatively low cost.
Furthermore, GO and rGO are processible and they can be fabricated or self-assembled
into macroscopic materials with controlled compositions and microstructures for practical
applications. GO is the precursor of rGO; thus, it plays a crucial role in controlling the
structure, property and the application potential of rGO. The pioneering work on the
synthesis of GO was reported by Brodie in 1859. In this method, one equal weight of
graphite was mixed with three equal weights of KClO3 and reacted in fuming HNO3 at 60
C for 4 days. Staudenmaier improved Brodie method by replacing about two thirds of
fuming HNO3 with concentrated H2SO4 and adding KClO3 in multiple portions. This
small modification enables the overall reaction in a single vessel; thus simplifying the
synthesis method. However, this reaction still needs a long time of 4 days. The most
important and widely applied method for the synthesis of GO was developed by Hummers
and Offeman in 1958 (Hummers method). In this case, the oxidation of graphite was
achieved by harsh treatment of one equal weight of graphite powders in a concentrated
H2SO4 solution containing three equal weights of KMnO4 and 0.5 equal weight of
NaNO3. The Hummers method, at least, has three important advantages over previous
techniques. First, the reaction can be completed within a few hours. Second, KClO3 was
replaced by KMnO4 to improve the reaction safety, avoiding the evolution of explosive
ClO2. Third, the use of NaNO3 instead of fuming HNO3 eliminates the formation of acid
fog [4].

Experimental Synthesis and purification

GO was prepared by the oxidation of natural graphite powder (325 mesh, Qingdao
Huatai Lubricant Sealing S&T Co. Ltd., Qingdao, China) according to Hummers method
with a modification of removing NaNO3 from the reaction formula. Typically, graphite

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powder (3.0 g) was added to concentrated H2SO4 (70 mL) under stirring in an ice bath.
Under vigorous agitation, KMnO4 (9.0 g) was added slowly to keep the temperature of the
suspension lower than 20 C. Successively, the reaction system was transferred to a 40 C oil
bath and vigorously stirred for about 0.5 h. Then, 150 mL water was added, and the
solution was stirred for 15 min at 95 C. Additional 500 mL water was added and followed
by a slow addition of 15 mL H2O2 (30%), turning the colour of the solution from dark
brown to yellow. The mixture was filtered and washed with 1:10 HCl aqueous solution
(250 mL) to remove metal ions. The resulting solid was dried in air and diluted to 600 mL,
making a graphite oxide aqueous dispersion. Finally, it was purified by dialysis for one
week using a dialysis membrane (Beijing Chemical Reagent Co., China) with a molecular
weight cut off of 800014,000 g mol1 to remove the remaining metal species. The resultant
graphite oxide aqueous dispersion was then diluted to 1.2 L, stirred overnight and
sonicated for 30 min to exfoliate it to GO. The GO dispersion was then centrifuged at 3000
rpm for 40 min to remove the unexfoliated graphite. For comparison, GO was also
prepared by conventional Hummers method, and purified using the same procedures
described above. The GO products prepared by the improved and conventional Hummers
methods are nominated as GO1 or GO2, respectively. 2.2. Instruments and
characterizations GO dispersions were freeze-dried and used for morphological and
structural characterizations. Raman spectra were recorded on a Renishaw Raman
spectrometer with a 514 nm laser at a power of 4.7 mW. X-ray photoelectron spectra (XPS)
were recorded on an ESCALAB 250 photoelectron spectrometer (ThermoFisher
Scientific) with Al Ka (1486.6 eV) as the X-ray source set at 150 W and a pass energy of 30
eV for high resolution scan. UV–visible spectra were taken out by the use of a U-3010
UV–visible spectrometer (Hitachi, Japan). Scanning electron micrographs (SEM) were
taken out on a field-emission scanning electron microscope (Sirion-200, Japan). The
atomic force microscopic (AFM) images of GO sheets were measured using a scanning
probe microscope (SPM-9600, Shimadzu). The samples used for SEM and AFM
characterizations were deposited on silicon wafers and mica sheets, respectively. Fourier
transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) spectra were
recorded on a Fourier transform infrared spectrometer (Bruker Vertex V70). The zeta

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potentials of GO aqueous dispersions were measured by the use of HORIBA Nano particle
analyser SZ-100. X-ray diffraction (XRD) was carried out on a D8 Advance X-ray
diffractometer with Cu Ka radiation (k = 0.15418 nm, Bruker, Germany). 2.3. The
removing of Mn2+ ions from waste water Typically, waste water was collected from the
process of filtrating GO from the reaction system of improved Hummers method.
Successively, 20 mL of waste water was diluted and neutralized by a 0.2 g mL1 KOH
solution. The pH of the solution was adjusted to 10 and a precipitate was formed. Then, this
system was kept undisturbed overnight to age the precipitate. Finally, the sediment was
filtrated. The Mn2+ ions in the purified waste water (or filtrate) was test by adding it for
several drops into a 3 mL aqueous solution of Na2S2O8 (0.1 g mL1 ) followed by boiling
the mixture for 1 min.

GO samples were synthesized by using Hummers method without (GO1) or with

(GO2) using of NaNO3 and purified by dialysis and centrifugation. The yields (the weight
of GO divided by the weight of graphite powder) of GO1 and GO2 were measured to be
92% ± 3% and 96% ± 2%, respectively. This result indicates that the solution of
concentrated H2SO4 containing KMnO4 is capable of oxidizing graphite to GO in a yield
close to that of Hummers method even without the assistance of NaNO3.

We developed an improved Hummers method without using NaNO3 for the synthesis
of GO. This improved method eliminates the generation of toxic gasses and simplifies the
procedure of purifying waste liquid, thus decreases the cost of GO synthesis. The GO
products prepared by both the improved and conventional Hummers methods are nearly
the same in Fig. 5 – XRD pattern of the precipitation containing Mn. Fig. 2 – (a) Tapping
mode AFM and (b) SEM images of GO1. (c) XRD pattern, (d) 514.5 nm excited Raman
spectrum and (e) FTIRATR spectrum of freeze-dried GO1. Fig. 3 – TGA curves of
freeze-dried GO1 and GO2. Fig. 4 – Photographs and illustration of the post-treatment of
waste water. Insets show the pictures of colour test of Mn2+ ions. 228 CARBON 64 (2013)
225 – 229 their dispersibility, chemical structures, thicknesses, and lateral dimensions.
Furthermore, the exclusion of NaNO3 does not affect the yield of the overall reaction. The
improved Hummers method described here can be used to prepare GO in large scale and it

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is one-step towards the synthesis of graphene and its derivatives through environmentally
friendly approaches.

2.1.2 Chemical Vapour Deposition(CVD)

A. Moreno-Bárcenas, J. F. Perez-Robles, Y. V. Vorobiev, N. Ornelas-Soto, A.

Mexicano, and A. G. García

Compared with other methods, such as mechanical exfoliation of graphite,

liquid-phase exfoliation, and reduction of graphene oxide (GO), chemical vapor
deposition(CVD) is regarded as the most promising way for large-scale graphene
production at a large scale with low defects, good uniformity, and controlled number of
graphene layers, which has attracted intense research attention during the last decades.
CVD involves the activation of gaseous reactants and the subsequent chemical reaction,
followed by the formation of a stable solid deposit over a suitable substrate such as Ni, Cu,
Fe, Pt, or their alloys. As early as 1969, Robertson et al discovered that chemical vapor
deposition in the presence of methane produces a layer of graphite on some transition metal
surfaces. However, even if the prepared graphene displays excellent performance, it cannot
be applied to the related devices due to the limitations of deposition on the metal surface.
The advent of poly(methyl methacrylate)-mediated Nano transfer printing technology
enabled the successful transfer of graphene from the growth substrate to any other
substrate, and it also completely changed the status of chemical vapor deposition methods
in the preparation method of graphene. It is worth mentioning that, compared to exfoliated
graphene obtained from natural graphite, the CVD graphene still shows a lower carrier
mobility ranging from 100 to 1000 cm2 /(V⋅s), due to the presence of growth defects and
boundaries. Therefore, a feasible route to improve graphene film quality lies in increasing
the domain size that enables to avoid the side effect of graphene domain boundaries. Now,
large-area graphene synthesized have generally been single crystalline, and related
research is aimed to control the domain size, defects, number of graphene layers, and so on.
With regard to desired graphene, there are many effect parameters including hydrogen,
oxygen, gas flow rate, and residence time [5].

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Polycrystalline copper foils of quality electrolytic industrial (C-1100) with a size of 15

× 30 cm and purity of 99.9% w/w were used as substrates. The copper was washed with
plenty of acetone and cleaned with wipes to remove grease and dust. Acetylene gas was
used as carbon precursor with 98% concentration. High purity nitrogen gas was used for
getting a neutral atmosphere and a high purity 90 : 10 mixture of N2 : H2 gases were used
to obtain reducing conditions inside the reactor and before the graphene deposition. A
conventional CVD reactor provided with an inverted compressor was used in order to
facilitate the gas expulsion. 2.2. Growth Process. The studied parameters were temperature
and flow rate of carbon precursor. In brief, a few Journal of Nano materials 3 Precursors
Copper substrate (polycrystalline) Heat source Gas at steady state Of (a) proposed method
at atmosphere pressure using polycrystalline substrate and gas discontinuous flow and (b)
traditional process at high vacuum using mono crystalline substrate and gas continuous
flow. of N2 gas was introduced into the reactor for 15 min to remove the present oxygen.
Ten 1 L/min of N2/H2 was introduced to reduce the copper oxides in the surface of the
sheet. Afterwards, on the one hand, acetylene was injected to the reactor at constant flow
rate for 1 min. The injection was stopped in order to start the graphene growth process with
the gas trapped inside reactor at different temperatures. The cooling down was carried out
under nitrogen atmosphere with a ramp of 8∘ C/min. Graphene layers were analysed in a
high-resolution transmission electron microscope (HRTEM) JEOL-JEM 2200FS equipped
with a spherical aberration corrector in the condenser lens and operated at 200 kV. Images
were acquired in STEM mode, with bright field (BF) and high angle annular dark field
(HAADF) detectors. Also, atomic force microscopy (AFM) was used, Asylum, model
MFP3D-SA, using the technique of noncontact mode or AC, with rectangular cantilever
model AC240TS-R3 at 2 N/m and a scanning speed of 70 kHz. The Raman spectra of
graphene layers on copper substrate were recorded using a Renishaw in Via Raman
spectrometer with an electronically cooled (−70∘ C) CCD camera and a Leica microscope.
The excitation source used was a He-Ne laser with emission at 633 nm; integration time
was 10 seconds. A diffraction grating at 1200 lines/mm and objective of 50x magnification
with numerical aperture of 0.75 were used.

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Graphene Synthesis by CVD. An overview of CVD processes used with different gas
precursors and growth conditions. Unlike the conditions mentioned in Table 1, our process
allows the graphene synthesis, in a maximum time of 66 min, without making use of
vacuum pumps. Note that for similar times of synthesis, pressures of 3–9 × 10−2 torr are
evaluated temperatures for the growth process. Heating Cleaning Growth Cooling ( ∘ C)
Time Flow rate C2H2 (scum) Reaction time 1000∘ C 30 min 100 5 min 30 900∘ C 30 min
100 5 min 30 800∘ C 30 min 100 5 min 30 required in most of the processes reported in
Table 1 while atmospheric pressure is used in ours. Also in our process N2 is used as
carrier gas instead of using argon, which is more expensive. The proposed synthesis
method is compound by four stages (cleaning, precursor injection, reaction time, and
cooling). The temperature and flow rate of carbon precursor were the studied parameters.
In Figure the traditional process and differences with our process are shown. In the first
stage, the process temperatures 800, 900, and 1000∘ C. The objective was to know the
temperature at which amorphous carbon is formed and avoid it in the following tests. A
flow rate at 100 scum of acetylene was used as reference. In the second stage, acetylene gas
flow rate was tested at 100, 80, 30, and 10 scum as shown in Table 3. The heating
temperature was fixed after obtaining the results being 1000∘ C, the temperature which
avoids the amorphous carbon deposition.

The method described in this work offers important advantages such as the number of
parameters was simplified; time of synthesis is shorter than those used in traditional
methods; it is a low-cost method when compared to those that using a continuous gas flow
rates; the proposed process in batch, besides using lower gas consumption, represents a
significant reduction of emissions in the environment besides, the use of electrolytic
technical grade copper instead of mono crystalline copper (reagent grade or high purity
cooper foil) also contributes to reducing costs; finally, the use of a mixture of N2/H2 (90 :
10) instead of pure H2, decreases the explosive risk by gas accumulation. In general, the
synthesized graphene shows a good quality with spectral characteristics very near to the
monolayer graphene; therefore, the obtained material with the proposed method represents
an attractive option for industrial purposes or graphene mass production.

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2.1.3 Liquid Phase Exfoliation

Yanyan Xu, Huizhe Cao, Yanqin Xue, Biao Li and Weihua Cai

Graphene, a two-dimensional (2D) carbon nano material, has attracted worldwide

attention owing to its fascinating properties. One of critical bottlenecks on some important
classes of applications, such as printed electronics, conductive coatings, and composite
fillers, is the lack of industrial-scale methods to produce high-quality graphene in the form
of liquid suspensions, inks, or dispersions. Since 2008, when liquid-phase exfoliation
(LPE) of graphene via sonication was initiated, huge progress has been made in the past
decade. This review highlights the latest progress on the successful preparation of
graphene in various media, including organic solvents, ionic liquids, water/polymer or
surfactant solutions, and some other green dispersants. The techniques of LPE, namely
sonication, high-shear mixing, and micro fluidization are reviewed subsequently.
Moreover, several typical devices of high-shear mixing and exfoliation mechanisms are
introduced in detail. Finally, we give perspectives on future research directions for the
development of green exfoliation media and efficient techniques for producing
high-quality graphene. This systematic exploratory study of LPE will potentially pave the
way for the scalable production of graphene, which can be also applied to produce other 2D
layered materials, such as BN, MoS2, WS2, etc [6].

Techniques of Liquid-Phase Exfoliation

Traditionally, LPE includes mainly two different exfoliation techniques of graphite

cavitation in sonication and shear forces in high-shear mixer. Recently, micro fluidizer has
been proven efficient to exfoliate graphite in suitable aqueous solutions under high shear
rate. LPE is a straightforward Nano materials 2018, 8, 942 5 of 32 procedure with high
potential for the mass production of graphene. The basic devices of sonication or
high-shear mixing are generally available. In addition, the operating conditions of LPE are
mild and do not require vacuum or high temperature systems. However, the large-scale
application of sonication assisted LPE has been hindered because of the low concentration
of graphene and the high energy consumption during the production process. The

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high-shear mixing or micro fluidizer method is an emerging LPE technology, which can
exfoliate graphite successfully using high-shear mixer-driven fluid dynamics.

It is now well-acknowledged that one of critical bottlenecks on some important

classes of applications—such as printed electronics, conductive coatings, and composite
filler is the lack of industrial-scale methods to produce high-quality graphene in the form of
liquid suspensions, inks, or dispersions. LPE is just a promising cost-effective method for
scalable production of single or few-layer graphene through simple and available devices.
Since 2008, when LPE of graphite powder via the sonication was first initiated, huge
progress has been made in the past decade. Sonication-assisted LPE has been widely used
to prepare the dispersions of graphene but suffers from high energy-extensive consumption
and low efficiency. Fortunately, the appearance of high-shear mixing and micro
fluidization recently brings new vitality to the development of LPE. Nano materials 2018,
8, 942 26 of 32 This review has highlighted the latest progress on the successful
preparation of graphene in various media, including organic solvents, ionic liquids,
water/polymer or surfactant solutions, and some other green dispersants. The techniques of
LPE, namely, sonication, high-shear mixing and micro fluidization have also been
reviewed subsequently. Moreover, several typical devices of high-shear mixing and
exfoliation mechanisms were also introduced in detail. This systematically exploratory
study of LPE will pave the way for the scalable production of graphene, which can be
applied to produce other 2D layered materials, such as BN, MoS2, WS2, etc. However, it is
still an enormous challenge to achieve fundamental goals of commercial availability of
massive high-quality graphene with cost-efficient and environmentally friendly LPE.
There are multitudinous conundrums to be further studied and overcome, some of which
and our perspectives are discussed as follows: The yield of LPE is still too low to meet the
microscopical requirement of industrial application of graphene, and the production of
single-layer, large-size graphene is a huge challenge as well. The amount of available
solvents that are propitious to LPE of graphene is limited. In addition, most solvents that
can be used to disperse graphite are relatively expensive and toxic. Polymers or surfactants
as dispersants are challenging to be removed, which results in the poor performance of the

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graphene prepared by polymer- or surfactant-assisted LPE. Sonication or shear exfoliation

generally result in the reduction of the size of graphene nano sheets. The devices of high
shear mixing are utilized directly from other fields of science, there is no equipment wholly
designed for LPE. Graphene nano sheets prepared by LPE tend to aggregate easily and
irreversibly in most solvents due to van der Waals forces and high surface energy, so
separating graphene from the dispersion is another important issue. More importantly,
there is a more basic and systematic understanding of the advanced LPE mechanisms,
which would lead to more innovative ideas about new and more efficient methods. Though
the specified centrifugation strategy can separate the graphene dispersions with different
average sheet size, the method cannot solve the fundamental problem, i.e., the
uncontrollable size of graphene nano sheets obtained by LPE. The exploration of new
green cost-efficient exfoliation media and techniques to increase the exfoliation efficiency
of graphite is urgent and vital; The pre-treatment of the starting materials may be very good
way, such as the conversion of graphite into graphite intercalation compounds or direct
exfoliation in pure water by controlling the conditions of exfoliation, such as temperature
and pressure, which can not only prevent the agglomeration of the nano sheets, but also
simplify the exfoliation process or increase the yield of graphene. The stirred-tank reactor,
a common equipment in chemical industry, may be effective when applied to exfoliate
graphene. The combination of high-shear mixing with chemical methods or supercritical
fluid techniques may further improve the efficiency of exfoliation or the quality of
graphene. The method of molecular dynamic simulation can be used to further explain the
advanced mechanisms for optimizing.

2.2 Electrochemical synthesis process

Xiao-Miao Feng , Rui-Mei Li , Yan-Wen Ma , Run-Feng Chen , Nai-En Shi , Qu-Li

Fan

This work describes a new one-step large-scale electrochemical synthesis of

graphene/polyaniline (PANI) composite films using graphite oxide (GO) and aniline as the
starting materials. The size of the film could be controlled by the area of indium tin oxide

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(ITO). Scanning electron microscopy (SEM), transmission electron microscopy (TEM),

X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR),
and ultraviolet–visible absorption spectrum (UV–vis) results demonstrated that the
graphene/PANI composite fi lm was successfully synthesized. The obtained
graphene/PANI composite film showed large specific area, high conductivity, good
biocompatibility, and fast redox properties and had perfect layered and encapsulated
structures. Electrochemical experiments indicated that the composite film had high
performances and could be widely used in applied electrochemical fields. As a model,
horseradish peroxidase (HRP) was entrapped onto the film-modified glassy carbon
electrode (GCE) and used to construct a biosensor. The immobilized HRP showed a pair of
well-defined redox peaks and high catalytic activity for the reduction of H2O2 .
Furthermore, the graphene/ PANI composite film could be directly used as the super
capacitor electrode. The super capacitor showed a high specific capacitance of 640 F g − 1
with a retention life of 90% after 1000 charge/discharge cycles [7].

We successfully synthesized graphene/PANI composite film in large scale by a

facile electrode position method by using GO and aniline monomer as the starting
materials. Based on the large specific area, high conductivity, good biocompatibility, and
fast redox properties of the graphene/PANI composite film, HRP was entrapped onto the
film-modified electrode and applied to construct a H2O2 biosensor. The biosensor
exhibited a fast aerometric response (5 s), a good linear response over a wide range of
concentrations from 1.0 × 10 − 6 to 1.6 × 10 − 4M , and a low detection limit of 0.8 × 10 −
7 M . Furthermore, the biosensor had satisfactory stability and good reproducibility. To
broaden the applications of nano materials in applied electrochemical fields, a super
capacitor was also constructed based on the composite film. The super capacitor showed a
high specific capacitance of 640 with a retention life of 90% after 1000 charge/discharge
cycles. This method developed in this work opens up a general route to prepare a wide
range of graphene-based nano composite materials with broad application prospects.

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CHAPTER 3

SCOPE OF THE WORK

3.1 Problem Definition

Today, a new material has the potential to alter the future. Dubbed a “super
material,” graphene has researchers the world over scrambling to better understand it.
Graphene is a two-dimensional carbon allotrope with the carbon atoms arranged in a
two-dimensional honeycomb lattice and Graphene’s incredible strength despite being so
thin is already enough to make it amazing, however, its unique properties do not end there.
It is also flexible, transparent, highly conductive, and seemingly impermeable to most
gases and liquids. It almost seems as though there is no area in which graphene does not
excel. Due to these reasons, it is one of the most promising nano materials and is being
considered in a wide range of applications ranging from optics to electronics. Despite this,
graphene is also one of the strongest materials in the known universe. With a tensile
strength of 130 GPa (gigapascals), it is more than 100 times stronger than steel. For
synthesis of graphene we used the process called Electrochemical synthesis method of
synthesising graphene because this process has been proved to consume less time
compared to other method of synthesis and its also less cost there isn’t any complicated
steps.

3.2 Objective of the problem

Graphene’s long list of miraculous traits makes it seem almost magical, but it could
have very real and drastic implications for the future of physics and engineering.
Graphene’s atoms are arranged in a hexagonal arrangement. Interestingly, when graphene
is isolated from graphite it takes on some miraculous properties. It is a mere one-atom
thick, the first two-dimensional material ever discovered. Many methods have been used
for the synthesis of graphene but here we are using Electrochemical synthesis method of

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synthesising graphene which is economical to produce and easy to synthesis and it is one
step method.

Objectives are as follows:

1. Synthesis of Graphene by Electrochemical synthesis method.

2. Ammonium sulphate solution as a inorganic solution for the exfoliation of graphite.

3. Microstructural characterization of synthesised graphene by using SEM(Scanning

Electron Microscope), XRD(X-Ray Diffraction), EDAX(Energy-Dispersive
X-Ray spectroscopy).

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CHAPTER 4

METHODOLOGY AND EXPERIMENTATION

4.1 Materials

4.1.1 Graphite Rods

The main reason that graphite electrodes are used in electrochemical synthesis is
that graphite is an excellent conductor and graphite is an allotropy of carbon and graphene
is also an allotropy of carbon, graphite is the only source of extracting graphene. The
structure of graphite is such that it has a large number of electrons floating freely between
the different layers of atoms (graphite bonds are formed of only three out of the four
electron shells of the carbon atom, leaving the fourth electron to move freely). These
electrons act as a powerful conductor, enabling the electrochemical synthesis process to
progress smoothly. In addition, graphite is economical, stable at high temperatures and
hard-wearing. For all these reasons, graphite electrodes are frequently used in
electrochemical synthesis.

The atomic structure of graphite results in a large number of electrons not being
bonded, allowing them to migrate between the layers of graphite from this we can easily
extract graphene. It is this large number of free electrons (electron delocalization) that give
graphite its excellent conductive properties. As well as being a good conductor, graphite is
also cheap, robust and easily accessible – all further reasons why it’s commonly used as an
electrode in synthesising graphene.

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Table 4.1: Mechanical and Physical properties of Graphite

Property Graphite
Crystal structure Hexagonal
Orbital Hybridisation sp2
Density 2.267 g cm-3
Heat capacity 8.517 J mol-1 K-1
Thermal Conductivity -150 Wm-1K-1
Melting Point More than 3600℃
Modulus of Elasticity 8-15 Gpa
Compressive Strength 82 Mpa
Tensile Strength 25 Mpa

Fig 4.1: Graphite Rod

4.1.2 Ammonium Sulphate

Ammonium sulphate is an inorganic sulphate salt obtained by reaction of sulphuric

acid with two equivalents of ammonia. A high-melting (decomposes above 280℃) white
solid which is very soluble in water (70.6 g/100 g water at 0℃; 103.8 g/100 g water at
100℃), it is widely used as a fertilizer for alkaline soils. It has a role as a fertilizer. It is an

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ammonium salt and an inorganic sulphate salt. Ammonium sulphate is extremely soluble in
water due to its ionic nature.

Ammonium sulphate ppt. is a common method for protein purification by

precipitation. As the ionic strength of a solution increases, the solubility of proteins in that
solution decreases. Ammonium sulphate is extremely soluble in water due to its ionic
nature, therefore it can "salt out" proteins by precipitation. Due to the high dielectric
constant of water, the dissociated salt ions being cationic ammonium and anionic sulphate
are readily solvated within hydration shells of water molecules. The significance of this
substance in the purification of compounds stems from its ability to become more so
hydrated compared to relatively more non polar molecules and so the desirable non-polar
molecules coalesce and precipitate out of the solution in a concentrated form. This method
is called salting out and necessitates the use of high salt concentrations that can reliably
dissolve in the aqueous mixture. The percentage of the salt used is in comparison to the
maximal concentration of the salt in the mixture can dissolve. As such, although high
concentrations are needed for the method to work adding an abundance of the salt, over
100%, can also over saturate the solution, therefore, contaminating the non-polar
precipitate with salt precipitate.

IUPAC Name: Diazonium sulphate

Molecular Formula:(NH4)2SO4

Molecular Structure of (NH4)2SO4

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Table 4.2: Properties of Ammonium Sulphate

Property Ammonium Sulphate

Molecular Weight 132.14 g/mol
Melting point Above 280℃
Density 1.77 g/cm³
Appearance Fine white
Solubility in Water 70.6g per 100g of water
Flammability Not Flammable
pH 5.5

Fig 4.2: Ammonium Sulphate

4.1.3 DC Source

Direct current (DC) is the one directional or unidirectional flow electric charge.
An electrochemical cell is a prime example of DC power. Direct current may flow through
a conductor such as a wire, but can also flow through semiconductors, insulators, or even
through a vacuum as in electron or ion beams. The electric current flows in a constant

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direction, distinguishing it from alternating current (AC). A term formerly used for this
type of current was galvanic current.

Direct current may be converted from an alternating current supply by use of

a rectifier, which contains electronic elements (usually) or electromechanical elements
(historically) that allow current to flow only in one direction. Direct current may be
converted into alternating current via an inverter.

Direct current has many uses, from the charging of batteries to large power supplies
for electronic systems, motors, and more. Very large quantities of electrical energy
provided via direct-current are used in smelting of aluminium and
other electrochemical processes. It is also used for some railways, especially in urban
areas. High-voltage direct current is used to transmit large amounts of power from remote
generation sites or to interconnect alternating current power grids.

The main reason for using DC source is that we require a constant voltage of 10V,
while in alternating current the voltage sometimes fluctuates. In electrochemical synthesis
the voltage should not vary to get the desired results.

Fig. 4.3 DC Source

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Synthesis and characterization of Graphene by Electrochemical Process

4.2 Synthesis of Graphene

4.2.1 Preparation of Ammonium Sulphate solution

In Electrochemical synthesis we are using ammonium sulphate solution for the

synthesis of graphene. Here we are preparing 250ml of ammonium sulphate solution by
using ammonium sulphate and distilled water. The 0.5M ammonium sulphate is used to
prepare the solution.

Calculation to find out the amount of ammonium sulphate required to prepare

250ml of ammonium sulphate solution:-(0.5*132.15*250)÷1000=16.51g.

The 16.51g ammonium sulphate is measured and taken in a 250ml volumetric flask
and distilled water is added up to the 250ml mark and mixed until the salt completely
dissolved. This prepared ammonium sulphate solution is used for the graphene synthesis
process.

4.2.2 Experimental set up for electrochemical synthesis

The experimental set up consists of two graphite rods act as electrodes which are
connected to the anode and cathode of 10V DC power supply, the graphite rods are
immersed into the prepared ammonium sulphate solution. magnetic stirrer is used to stir
the solution uniformly so that graphene sheets were exfoliates into the electrolytic solution.

Fig. 4.4 Experimental set up

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Synthesis and characterization of Graphene by Electrochemical Process

The overall setup consists of graphite rods, ammonium sulphate solution, DC

source, filter paper for filtration process and oven for drying purpose.

4.2.3 Experimentation

Electrochemical synthesis is one step method to produce graphene, it is one of the

easiest way to produce graphene and also it is very economical one. For electrochemical
synthesis we require graphite rods, ammonium sulphate solution, DC source, filter paper
for filtration process and oven for drying purpose.

In Electrochemical synthesis two weighed graphite bars an anode and cathode were
immersed in the 0.5M ammonium sulphate solution and connected to the 10V DC power
supply and stirred continuously for 2 hours the graphene sheets were exfoliates into
electrolytic solution. As the graphite electrodes are connected to the 10V DC power supply
the anode graphite sheets start to exfoliate and the exfoliated product is graphene.

The obtained graphene is filtered by using filter paper with distilled water to
remove the foreign particle, the filtered graphene is subjected to the drying in the hot air
oven at 65 to 70℃ for 8 to 10 hours.

In graphene synthesis, the graphite electrode (thickness - 5 mm) was employed as

an electrode and source of graphene from electrochemical exfoliation. The graphite
electrode was used as both anode and cathode with a separation of 1.5cm. The 0.5 M
sulphuric acid was used as the electrolyte. The electro chemical exfoliation process was
carried out by applying DC on graphite electrode (10 V). To prepare the graphene sheet
suspension the exfoliated graphene sheets were collected with 0.2 µm PVDF membranes
filter and washed with DI water by filtration. After drying at 60°C, the material was then
used for further characterization and electrode preparation. All of these electro chemical
exfoliation experiments were performed at room temperature.

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Synthesis and characterization of Graphene by Electrochemical Process

Fig. 4.5 Electrochemical Synthesis Fig. 4.6 Filtration Process

Fig. 4.7 Anode and Cathode Fig. 4.8 Synthesised Pure Graphene

after experiment

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Synthesis and characterization of Graphene by Electrochemical Process

Table 4.3: Experimental tabular column.

Initial anode weight: 22.1034 g

Initial cathode weight: 31.004g

Voltage(volts) Current(Amps) Temperature(℃) Time(minutes)

3 0.06 37 3
7 1.43 27 6
7 3.72 35 12
10 3.81 40 20
10 3.99 41 30
10 4.01 42 40
10 4.04 43 50
10 3.99 43 60
10 4.11 46 70
10 4.05 44 80
10 4.03 45 90
10 3.95 44 100
10 3.99 45 110
10 3.97 44 120

Final anode weight: 20.3359g

Final cathode weight: 30.998g

The amount of anode dissolved=22.1034-20.3359=1.7639g of graphene

4.3 Microstructural Characterization

In this work, characterization is performance to determine the particle size,

morphology, structure and elemental composition. The chemical analysis is carried out by
Scanning Electron Microscopy(SEM), X-Ray Diffraction(XRD) and Energy Dispersive

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Synthesis and characterization of Graphene by Electrochemical Process

X-Ray Spectroscopy(EDAX).ssssThe fundamental principle and importance of the

instruments employed is discussed in this section.

Scanning electron microscopic (SEM) and X-ray diffraction (XRD) image of a

composite material contains visible morphological structures like clusters of its constituent
particles which are immiscible with the material base. These structures generally are
attributed in terms of their shapes and sizes. Through proper analysis of SEM image, we
can quantify shape and size of the morphological structures more accurately. SEM image
analysis of material like polymer composite reveals its several morphological as well as
mechanical properties. A polymer composite is a combination of a polymer matrix and a
strong reinforcing phase - the filler. A polymer nano composite is a polymer matrix with a
reinforcing phase consisting of particles with one dimension in the nano-sized regime.

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CHAPTER 5

RESULTS AND DISCUSSION

5.1 Graphene Synthesis

Graphene is an allotrope of carbon in the form of a single layer of atoms in a

two-dimensional hexagonal lattice in which one atom forms each vertex, graphene has
emerged as one of the most promising nonmaterial because of its unique combination of
superb properties. About 15.66g of graphene was produced by the process of
Electrochemical Synthesis.

Properties:

Appearance : Black Powder

Thickness : 5-10nm

Number of layers : 5-7

Tensile Strength :130 Gpa

Young’s modulus : 1 TPa

Specific Surface area : 2630 m2/g

Density : 2267 Kg/m3

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Synthesis and characterization of Graphene by Electrochemical Process

Fig.5.1 Pure Graphene

In this work, characterization is performance to determine the particle size,

morphology, structure and elemental composition. The chemical analysis is carried out by
Scanning Electron Microscopy(SEM), X-Ray Diffraction(XRD) and Energy Dispersive
X-Ray Spectroscopy(EDAX). The fundamental principle and importance of the
instruments employed is discussed in this section.

5.2 Scanning Electron Microscope(SEM)

A scanning electron microscope (SEM) is a type of electron microscope that

produces images of a sample by scanning the surface with a focused beam of electrons.
The electrons interact with atoms in the sample, producing various signals that contain
information about the surface topography and composition of the sample.

Specimens are observed in high vacuum in conventional SEM, or in low vacuum or

wet conditions in variable pressure or environmental SEM, and at a wide range of
cryogenic or elevated temperatures with specialized instruments.

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Synthesis and characterization of Graphene by Electrochemical Process

Fig.5.2 SEM Images of graphene

5.3 X-Ray Diffraction(XRD)

X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for
phase identification of a crystalline material and can provide information on unit cell
dimensions. A typical wavelength used for X-ray experiments is 1.541Å. XRD is applied
extensively as the major ex-situ method to characterize metallic and ceramic
polycrystalline thin films.XRD is used to measure phase composition, Lattice constant,
Grain size, Stress & Strain, Dislocation density.

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Synthesis and characterization of Graphene by Electrochemical Process

Measurement Conditions:
Dataset Name 10-80-Powder

File name C:\Users\User\Desktop\10-80-Powder.ASC

Raw Data Origin ASCII-2Theta-Intensity (.ASC)

Scan Axis Gonio

Start Position [°2θ] 10.0250

End Position [°2θ] 79.9850

Step Size [°2θ] 0.0300

Scan Step Time [s] 1.0000

Scan Type Pre-set time

Offset [°2θ] 0.0000

Divergence Slit Type Fixed

Divergence Slit Size [°] 1.0000

Specimen Length [mm] 10.00

Receiving Slit Size [mm] 0.1000

Measurement Temperature [°C] 25.00

Anode Material Cu

K-Alpha1 [Å] 1.54060

K-Alpha2 [Å] 1.54443

K-Beta [Å] 1.39225

K-A2 / K-A1 Ratio 0.50000

Generator Settings 0 mA, 0 kV

Diffractometer Number 0

Goniometer Radius [mm] 240.00

Dist. Focus-Diverg. Slit [mm] 91.00

Incident Beam Monochromator No

Spinning No

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Synthesis and characterization of Graphene by Electrochemical Process

Main Graphics, Analyze View:

Counts
10-80-Powder

C1
8000

6000

4000

2000

C1
C1

C1
0
20 30 40 50 60 70

Position [°2θ] (Copper (Cu))

Fig.5.3 XRD pattern of graphene

Peak List:

Pos. [°2θ] Height [cts] FWHM Left [°2θ] d-spacing [Å] Rel. Int. [%]

26.4054 7317.94 0.2952 3.37543 100.00

42.3342 91.03 0.2362 2.13503 1.24
54.3885 385.44 0.3542 1.68692 5.27
72.4543 205.86 0.1771 1.30449 2.81
77.4112 95.11 0.3542 1.23287 1.30

Pattern List:

Visible Ref. Code Score Compound Displacemen Scale Factor Chemical

Name t [°2Th.] Formula

* 98-029-0661 67 Carbon 0.000 0.684 C1

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Synthesis and characterization of Graphene by Electrochemical Process

5.4 EDAX

Energy-dispersive X-ray spectroscopy, sometimes called energy dispersive X-ray

analysis or energy dispersive X-ray microanalysis, is an analytical technique used for the
elemental analysis or chemical characterization of a sample. It relies on an interaction of
some source of X-ray excitation and a sample.

Fig. 5.4 EDAX Image of Graphene

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Synthesis and characterization of Graphene by Electrochemical Process

CHAPTER 6

CONCLUSION AND FUTURE SCOPE

6.1 Conclusion

Good physical and mechanical properties make graphene as leading material for
future applications. It became subject of interest for researchers to explore and utilize its
properties for various applications ranging from civil to defence and aerospace
applications etc.

• High strength and modulus of graphene promises its application for

structural composite reinforcement.

• High surface area of graphene is also favourable for it as being utilized for
reinforcement.

• Lots of research has been done to discover physical properties of graphene.

It includes semiconducting behaviour, thermal conductivity, electrical
conductivity and some fundamental research related to basic theory of
physics.

• Fabrication techniques of alone single-layer graphene sheet have been

developed by various groups. Comparatively less work has been done to
demonstrate graphene as reinforcement for composite fabrication for
structural and other properties. Hence, it needs development of sounding
method for synthesis of graphene sheets in bulk amount.

• In current research some attempts were carried out to synthesize graphene

sheets in bulk amount and utilize it for composite fabrication.

• Bulk Graphite was used as raw material for synthesis of graphene. Various
kinds of exfoliation techniques were used to separate graphene planes apart
from each other. Raw materials were characterized by various techniques

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Synthesis and characterization of Graphene by Electrochemical Process

like silica and Fe content, particle size distribution, XRD analysis and FTIR
analysis.

• Raw materials were subjected to cleaning for removal of impurities like

silica and Fe. Graphite was washed by HF and again analysed for silica and
Fe content. Negligible amount of impurities were found which was difficult
to remove.

• XRD and FTIR analysis shows good orientation of graphite flakes with
presence of some functional groups attached to graphitic planes.

• In the very beginning, synthesis of graphene planes were attempted by

thermal exfoliation technique. It was carried out by intercalating graphite
by volatile substances which evaporates or decomposes rapidly producing
plenty of gases at high temperature. Acid mixture of H2SO4 and HNO3 was
used as one type of intercalants and FeCl3 was used as another type of
intercalant. Intercalated graphite was exfoliated by rapid heating at high
temperature mainly at 1000OC.

• Synthesized samples were characterized by various techniques like

volume expansion measurement, XRD and SEM etc.

• Exfoliated graphite by intercalating moderated amount of acid mixture

blended with IPA was found to result in highest volume expansion. SEM
shows very good degree of exfoliation showing good separation of planer
structure.

• XRD characterization confirms that along with it some trace amount of

planer stacking were found even upon exfoliation.

• In second method solution technique was used to functionalize graphitic

planes of graphite where functional groups are mainly oxygen containing
functionalities. Modified Hummer’s Method was utilized to get dispersion
of functionalized graphene in water. Dispersion of graphene oxide

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Synthesis and characterization of Graphene by Electrochemical Process

(graphene with oxygen containing functionality) was characterized by

various techniques.

• XRD analysis confirms significant increase in inter planer spacing of

graphitic planes from 3.34 Å to 8.44 Å because of functional groups
attached. Upon pyrolysis of above functionalized graphene it starts
regaining its original structure of graphite.

6.2 Future Scope

The present work comprises of synthesis of Graphene and development of

composites using these. A good amount of work was done and important conclusions have
been drawn. However, research is never ending task so more work can be done in future on
following lines.

• Interaction of graphene with matrix material can be improved by tailor

making changes in functionality.

• Utilization of exhaustive properties of graphene in composite with epoxy as

well as other matrix systems can result in more interesting research.

• Some extraordinary properties of graphene like quantum hall effect,

semiconducting effect etc. should be explored and utilized for other
application.

• High mechanical properties can lead graphene for good choice for
reinforcement in other composites like ceramics, metals etc. for structural
applications.

• As being high surface area material graphene can be used as good absorbent
for various materials in dry and dispersion form.

• Some changes with functionality can lead graphene as good candidate for
gas storage applications.

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REFERENCES
[1] The rise of graphene, A. K. GEIM and K. S. NOVOSELOV

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Chandwad, Nashik, India

[3] N.I. Zaabaa , K.L. Fooa, U. Hashima, S.J.Tanb,c, Wei-Wen Liua , C.H. Voona has
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nano-graphitic carbon for making high-performance electrochemical micro-sensors

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