INTERNSHIP REPORT ON REVIEW ON

GRAPHENE SYNTHESIS USING ELECTROCHEMICAL METHODS

III YEAR B-TECH

IN

CHEMICAL ENGINEERING
Submitted by

P.USHA RANI (N150347)

B.MAHALAKSHMI(N150468)
S.JAYARAJU(N150507)

G.YAZNA PRIYA(N151212)

Under the esteemed guidance

of Asst .Professor

Mrs.P.MYTHILI

DEPARTMENT OF CHEMICAL ENGINEERING

RAJIV GANDHI UNIVERSITY OF KNOWLEDGE TECHNOLOGIES

NUZVID, KRISHNA DIST-521202

 RAJIV GANDHI UNIVERSITY OF KNOWLEDGE TECHNOLOGIES

NUZVID, KRISHNA (521202), ANDHRA PRADESH

DEPARTMENT OF CHEMICAL ENGINEERING

DECLARATOIN CERTIFICATE

This is to certify that the thesis entitled “ GRAPHENE SYNTHESIS USING

ELECTROCHEMICAL METHODS ” submitted P.USHA RANI(N150347),
B.MAHALAKSHMI(N150468), S.JAYARAJU(N150507) and G.YAZNA PRIYA(N151212)
to the Department of Chemical Engineering Rajiv Gandhi University of Knowledge
Technologies, Nuzvid for the submission of internship project report in III year B-Tech in
Chemical Engineering is a bonafide work carried out under our supervision and guidance during
the academic year 2019
.This report is ,in our opinion ,is worthy of consideration for the Degree of Bachelor of
Technology in Chemical Engineering in accordance with the regulations of the unit.

Mr.M.Madhu Sudhan Reddy , Project supervisor

Assistant Professor, Mrs.P.MYTHILI

Head of the Department, Assistant Professor,

Dept.of chemical engineering, Dept.of chemical

engineering. RGUKT NUZVID.

 RAJIV GANDHI UNIVERSITY OF KNOWLEDGE
TECHNOLOGIES

NUZVID, KRISHNA (521202), ANDHRA PRADESH

DEPARTMENT OF CHEMICAL ENGINEERING

DISSERTION APPROVAL CERTIFICATE

This is to certify that the thesis entitled “ GRAPHENE SYNTHESIS USING
ELECTROCHEMICAL METHODS ”submitted P.USHA RANI(N150347),
B.MAHALAKSHMI(N150468), S.JAYARAJU(N150507) and G.YAZNA PRIYA(N151212)
to the Department of Chemical Engineering ,Rajiv Gandhi University of Knowledge
Technologies, Nuzvid for the award of Bachelor of Technology in chemical engineering has
been accepted by the External Examiners and that these students are successfully defended the
project viva in the Viva-Voice Examination held today

External Examiner
 ACKNOWLEDGEMENT

We would like to acknowledge and express our gratitude to the following people for their
magnificent support in sharing their wisdom and knowledge to my successful completion of
internship project.

We are very thankful to our guide Mrs.P.MYTHILI, Assistant Professor, Dept. of Chemical
Engineering and for his valuable inputs, motivation and persistence guidance throughout my
internship project.

We are sincerely thankful to our HOD, Asst.Prof.Mr.M.MADHU SUDHAN REDDY SIR,

Head of the Department of Chemical Engineering, for him immense cooperation and guidance.

We are thankful to the director Dr. SURYA CHANDRA RAO SIR for giving opportunity to do
this project.
 CONTENTS

TITLE
PAGE NO.
ABSTRACT……………………………………………………………………
LIST OF TABLES…………………………………………………………….

INTRODUCTION TO GRAPHENE .……………………………………

CHARACTRIZATION TECHNIQUES …………………………………

SYNTHESIS METHODS OF GRAPHENE………………………………..

Top-down methods…………………….

Bottom-up methods…………………….

FEED STOCKS FOR GRAPHENE SYNTHESIS……………………………..

INDUSTRIAL IMPLEMENTAION…………………………………………….

PARAMETERS AFFECT THE GRAPHENE………………………………….

NON-ELECTRIFIED ELECTROCHEMICAL EXFOLIATION METHOD……..

RECENT PROGRESS IN ELECTROCHEMICAL EXFOLIATION………..

APPLICATIONS…………………………………………………………………...

CONCLUSION……………………………………………………………………..

REFERENCES……………………………………………………………………….
 ABSTRACT

Among various materials, graphene has received substantial research attention due to its
captivating properties. The multidisciplinary characteristics of graphene have a wide range of
applications from health to aerospace.The graphene research has been directed towards the
consideration of new graphene derivatives and their utilisations for fabrication of products and
devices .In this review paper, we highlight the most important experimental results on the
synthesis of graphene material by electrochemical exfoliation.The literature data supported that
synthesis routes such as oxidative exfoliation-reduction, liquid-phase exfoliation and chemical
vapor deposition have the potential to be commercialized due to their ability to produce large
amount of high quality graphene.Graphene was characterized based on the c/o
ratio,defects,number of layers.Finally examine the how parameters like temperature, pressure,
voltage ,electrolyte, electrode, concentration, sonication time effect on production of graphene.

Keywords:Graphene, Electrochemical exfoliation, Graphene

oxide,Characterization,Synthesis methods.
 INTRODUCTION TO GRAPHENE

Graphene is composed of carbon atoms.Carbon is the sixth element in the periodic table with six
electrons surrounding its nucleus typically the four electrons and carbon outer orbitals form
covalent bonds with other atoms.When carbon forms compounds or is arranged in a crystal
structure,elemental carbon is the sixth most abundant element on earth and due to its abundance
its capacity to form diverse organic compounds and its unusual ability to form long chains of
covalent bonds,carbon serves as a common element of all known life.Carbon is stable in various
multi atomic structures including coal,diamond,graphite and several others.Graphite is a
crystalline allotrope of carbon,the most stable allotrope under standard conditions,it occurs
naturally in igneous rock as well as meteorites.The structure of graphite is best understood as a
stack of weakly bonded 2 D atomic lattices.Each lattice is considered single layer and
individually the layers are referred to as graphene.

Graphene was discovered by Konstantin Novoselov and Andrei Geim in 2004 and was
awarded nobel prize in 2010.Graaphene is a 2D single layer of carbon atoms with the hexagonal
packed structures.The carbon bonds are sp2 hybridized,where the in-plane 𝜎c-c bond is one of the
strongest bonds in materials and the out-of-plane 𝛱 bond,which contributes to a delocalized
network of electrons,is responsible for the electron conduction of graphene and provides the
weak interaction among graphene layers or between graphene and substrates.With these unique
structural characteristics,graphene has shown exceptional physical properties which have
attracted enormous research interest in both scientific and engineering communities.One of the
most remarkable properties of graphene is that its charge carriers behave as massless relativistic
particles or Dirac fermions and under ambient conditions they can move with little
scattering.This unique behaviour has led to a number of exceptional phenomena in graphene.

First,graphene is a zero bandgap 2D semiconductor with a tiny overlap between valence and
conduction bands.Second,it exhibits a strong bipolar electric field effect so that the charge carrier
concentrations of upto 1013 cm-2 and room temperature mobilitie of ∼ 10000 cm-2 s-1 are
measured.Third,an unusual half-integer Quantum Hall Effect(QHE) for both electron and hole
carriers in graphene has been observed by adjusting the chemical potential using the electric field
effect.In addition,graphene is highly transparent,with an absorption of ∼2.3% towards visible
light.Its thermal conductivity k,is measured with a value of ∼ 5000 WmK-1 for a single-layer
sheet at room temperature.Graphene also possesses excellent mechanical strength.
 The intrinsic mechanical properties of free-standing monolayer graphene membranes were
measured by nano-indentation in an atomic force microscope.The breaking strength is 42Nm-1
and the Young’s modulus is 1.0 TPa,indicating it is one of the strongest materials ever
measured.In graphite,the adjacent graphene layers are bound by weak van der Waals
forces.Therefore,the pristine graphene can be obtained from the mechanical exfoliation of
graphite using adhesive tapes.The bottom-up growth of graphene sheets is an alternative to the
mechanical exfoliation of bulk graphite.Chemical vapor deposition (CVD) has been used to grow
single and few-layer graphene sheets on metal surfaces,such as Ni and Cu.Large area epitaxial
graphene films upto a few micrometers in size can be subsequently transferred to other
substrates.Carbon segregation can also become graphene layers on carbon-containing
substrates,such as SiC,through high temperature annealing .However these methods are
impractical for large-scale solution based processes.Therefore,the oxidation and exfoliation of
graphite oxide,followed by the chemical reduction has been used to prepare reduced graphene
oxide (rGO) sheets or chemically functionalized graphene (CFG).

Besides the reduction with chemical agents,electrochemical,photochemical and thermal

reduction methods have been developed as well.As a precursor of rGO,graphene oxide (GO)
sheets,exfoliated from graphite oxide are obtained by the Hummers method,via the reaction of
graphite with a mixture of KMnO4 and concentrated H2SO4.GO sheets are thus highly oxidized
and characterized by the dominant presence of epoxides,alcohols and carboxylic acid
groups.These functional groups render GO and rGO advantageous compared to the pristine
graphene,in terms of the tunability in electrical and optical properties via chemical reactions.

Besides the graphene -based 2D sheets,other graphene related materials have been
fabricated as well,such as zero dimensional (0D) graphene quantum dots,1D graphene
nanoribbons (GNMs.These materials are expected to posses different electrical and optical
properties,due to the variation in size and geometry,and the presence of a large amount of edge
defects.Featuring unique physical and chemical properties and having reliable synthetic methods
for both solid and solution- phase processes,graphene and its derivatives have been incorporated
into a number of functional materials to form composites and have been used as building blocks
for various kinds of applications including photovoltaic devices,photocatalysis,sensors,cell
cultures,intracellular imaging and matrices for matrix-assisted laser desorption.

CHARACTRIZATION TECHNIQUES
Graphene properties such as Morphological, textural, surface chemistry and other
physicochemical attributes have been investigated.

1. Scanning electron microscopy (SEM):

Scanning electron microscopy is a technique used for examining the morphology of Graphene
and its derivatives. In this analysis, highly energetic electrons are applied to produce SEM
images of the sample. The Graphene material is placed on a silicon wafer of specific thickness
For SEM scanning and the number of layers can be estimated based On the color depth.

2. Atomic force microscopy (AFM):

Atomic force microscopy can be used to measure the Thickness, surface roughness and other
morphological features of Graphene and its derivatives. This technique has difficulty scanning
bulky material and only provides topographical images. It is unable to accurately distinguish the
number of layers of Graphene. The measured thickness of a single layer graphene by AFM
varied between 0.4–1.7 nm which differs substantially from the theoretical thickness of 0.34 nm.
The discrepancy is due to the Surface interactions, image feedback settings and surface
chemistry. A new AFM imaging mode to accurately determine the thickness Of graphene by
reducing the error from within 0.1–1.3 nm to 0.1–0.3 nm.

3. Transmission electron microscope (TEM):

Transmission electron microscope is commonly used to Analyze graphene due to its ability to
image the material at Atomic level. In TEM, a very high voltage of electron is transmitted
Through the thin sample and the signal produced is further analyzed. TEM is used to identify the
extent of defects, vacancy, dislocations and Stone-Wales rotation of graphene. High resolution
TEM (HRTEM) can be used to determine the thickness, number of layers and cross-sectional
view of folded graphene sheets At different locations. In TEM images, monolayer graphene
sheets Are displayed as transparent sheets while multi-layered graphene Sheets are shown as
multiple dark lines when the folded graphene Sheets are placed parallel to the electron beam.

4. X-ray diffraction (XRD) :

The crystallinity, atomic arrangement and crystal size can be Investigated by X-ray diffraction
(XRD) or X-ray crystallography. A crystalline material can be classified by its orderly and
continuously repeating arrangement in the atomic planes. A unique Diffraction pattern is formed
when X-rays are emitted on a crystalline material from the XRD. Additionally, the distance
between the atomic planes can be calculated by the Bragg’s Law. Each Crystalline material has a
unique XRD pattern which can be used as A fingerprint reference for material identification.

Fig.no.1 XRD for graphene

5. Raman spectroscopy :

Raman spectroscopy is an essential analytical technique for Graphene characterization. The

carbon material has distinctive Raman peaks known as D-, G- and 2D-peaks at approximately
1350,1580 and 2700 cm−1, respectively. Generally, the G-peak refers to The tangential
stretching mode of highly oriented pyrolytic Graphite whereas the D-peak represents the disorder
in sp2 hybridized carbon atoms (lattice distortion) and the 2D-peak is the Second order Raman
scattering process. The intensity ratio of D-Peak to G-peak (ID/IG) can be used to determine the
degree of Disorder in the graphene sample.

6. Fourier transform infrared spectroscopy (FTIR):

Fourier transform infrared spectroscopy is a method used For the determination of chemical
functional groups in graphene And its derivatives. Typically, graphite has characteristic peaks at
3430 and 1610 cm−1 corresponding to O–H stretching of adsorbed Water and skeletal vibration
from graphitic domains of aromatic C = C, respectively. In comparison to the graphite spectrum
the GO spectrum has new peaks at 1785 and 1707 cm−1 And 1105 cm−1 indicating the existence
of oxygen functional groups in the sample. Moreover, the Peak shift from 1610 (in graphite
spectrum) to 1625 cm−1 shows the successful incorporation of oxygenous functional groups into
graphite after oxidation. The rGO spectrum reportedly displayed a relatively low peak intensity
at 3430 cm−1 And disappearance of peaks at 1785, 1707 and 1105 cm−1 which Suggested the
occurrence of reduction of GO.
7.X-ray photoelectron spectroscopy (XPS):

X-ray photoelectron spectroscopy (XPS) is commonly used to Determine the relative amount of
carbon, oxygen and other Functional groups present in graphene materials . It is relatively
Accurate in determining the amount of C and O in the graphene Sample, particularly GO, as it is
difficult to fully dehydrate GO. XPS also provides information on the local binding environment
of a certain species for better understanding of the surface chemistry of the carbon material.

8.Brunauer-Emmett-Teller (BET) :

Brunauer-Emmett-Teller (BET) surface area analysis is an advanced technique employed to

determine the specific surface area And pore size distribution of graphene and its derivatives.
Generally, graphene has a large theoretical specific surface area which Provides surface
interactions between graphene and other materials.

SYNTHESIS METHODS OF GRAPHENE

Graphene should Be produced at a cost competitive to that of current materials. It is Of great

challenge to develop synthesis processes with the following attributes: cost effective, highly
reliable and scalable production as well as high product yield and quality.

The synthesis of graphene can be performed by two main

approaches: 1.top-down (destruction) Method

2.bottom-up (construction)Method

1. TOP-DOWN APPROCHE

Top –Down approach also known as destruction approach. This Type of methods such as
Mechanical exfoliation, arc discharge, Oxidative exfoliation reduction, Liquid phase exfoliation
and Unzipping of CNT.
 Fig.no.2 synthesis methods2 .

1. Mechanical Exfoliation:

Mechanical exfoliation can be categorized based on directional Routes such as normal force and
shear force vectors . One Of the recent studies on the normal force synthesis route is the Peeling
of graphite using advanced machinery of ultra-sharp single Crystal diamond wedge . This
method eliminates the need for Manual operation, and saves time and labor cost. Another method
Uses a three-roll mill machine, an established technique in rubber Industry, to produce graphene
of 1.13–
1.41 nm . The major Drawback of this method is the cost of adhesives such as polyvinyl Chloride
(PVC) and the purification of graphene from the adhesive. The removal of PVC was achieved by
heating in a muffle furnace At 500 °C for 3 h . Thus, residue PVC elimination could lead to High
energy consumption and hence high production cost. The two Approaches, however, still lack in-
depth synthesis and parametric Studies.

2. Arc Discharge:

Arc discharge, a conventional technology used for preparation Of fullerene and CNT , has been
found to be highly adaptable for graphene synthesis .the reaction chamber consists of an anode
(carbon precursor) and a cathode (graphite rod) which are submerged either in a gas or liquid
Medium. The applied electrical current dissociates the medium to Generate a high temperature
plasma reaching up to 3727–5727 °C, Sufficient to sublime the precursor . The synthesis of
graphene Has been investigated under different inert gas conditions which is generally expensive
due to the use of vacuum equipment. To Address this issue, low cost graphene was prepared by
using an air Medium in the arc discharge, instead of a H2/He medium

3. Oxidative exfoliation reduction:

Most GO are synthesized by oxidative exfoliation of graphite Followed by reduction to graphene

sheets or rGO. There are four Main routes for GO synthesis which include those of Brodie, Stau-
Denmaier, Hofmann and Hummers. Fig. 6 shows the reaction pathways of these methods which
occur at temperatures below 100 °C. The relatively low synthesis temperature is desirable to
Maintain low production cost. However, toxic gases such as nitrogen dioxide (NO2) and
dinitrogen tetroxide (N2O4) are generated By these methods . Thus, process safety and
environmental costs need to be considered during process scale-up. Currently,The Hummers
method is widely used for synthesis of GO as it is a Comparatively fast and safe process.
Moreover, it does not generate Explosive gases such as chlorine dioxide (ClO2) and acidic fog
with The use of potassium permanganate (KMnO4) and sodium nitrate (NaNO3) instead of
potassium perchlorate (KClO4) and nitric acid (HNO3) . Over the years, modification of the
Hummers method Has introduced a greener approach to producing GO. The synthesis of GO by
oxidative exfoliation of graphite and further reduction to rGO are associated with low production
cost and High yield. However, the rGO suffers from relatively low surface Area, poor electronic
conductibility, low solubility and irreversible Restacking of sheets due to van der Waals
attraction . Furthermore, there are uncertainties with the synthesis process such as Chemical
composition variation from the oxidation and reduction Processes, batch-to-batch reproducibility
and generation of permanent defects during the oxidation process. Even so, the advantages of
high scalability and low operation cost outweigh the Shortcomings of this method.

4. Liquid phase Exfoliation:

LPE, one of most widely used synthesis methods for graphene Production, was first introduced in
2008 .There are three main Steps in LPE synthesis:

(i) disperse graphite in a suitable solvent

(ii) exfoliate

(iii) purify the final products

Since LPE exfoliates graphite by overcoming van der Waals Force, the selection of a suitable
solvent is dependent on the liquid Properties such as surface energy, surface tension, Hildebrand
solubility and Hansen solubility parameters. Aqueous or non-Aqueous solvents with surface
energies within 70–80 mJ/m2 or surface tension within 40–50 mJ/m2 are ideal for graphite
exfoliation. The obtained information not only could Be used to produce high concentration of
graphene products in a Very small volume of solvent, but also to scale-up the process by
selecting less expensive, less hazardous and more stable solvents For graphene dispersion. Apart
from solvent selection, the modulation of sonication also Plays a crucial role to provide
appropriate cavitational effects for Exfoliation of graphite to generate single-layer graphene.
While LPE exhibits certain disadvantages, this process Is highly versatile in product synthesis
and functionalization, and Produces high quality graphene.

5. Unzipping Of CNT:

Unrolling or unzipping of CNT involves cutting of the cylindrical structure to lay flat the carbon
sheet into single, bi- or few-Layer graphene. Generally, unzipping of CNT requires a high strain
Rate (108–10/s) to break the C–C bond either in axial or longitudinal direction. CNT is
embedded in a polymer film such as Poly-methyl methacrylate (PMMA), and the matrix of
PMMA/CNT Is further peeled off in KOH before being exposed to argon (Ar) Based plasma.
This would lead to longitudinal fracture of the C–C bond of CNT. This method can produce
graphene with smooth Edges and narrow size distributions (10–20 nm) . Despite much interest in
This method, unzipping of CNT structure utilizes expensive precursors and chemicals.

2. BOTTOM-UP METHOD :

The bottom-up method is also called as construction method.These methods construct graphene
materials from atomic-sized precursors.The bottom-up methods include chemical vapor
deposition,epitaxial growth,substrate-free gas-phase synthesis,template route and total organic
synthesis.

6. Chemical vapor deposition (CVD):

CVD decomposes hydrocarbon gases (such as methane (CH 4),acetalyne (C2H2),ethylene (C2H4)
and hexane (C6H14)) and other biomass materials to grow graphene sheet on metallic catalysts at
elevated temperatures (650-1000oC).Upon contacting the hot surface of metal catalyst,the carbon
precursor dissociates into free carbon and hydrogen atoms.The carbon atom then diffuses
through the surface and the bulk of metal catalyst,and subsequently forms graphene sheet on the
metal surface upon reaching the carbon solubility limit.To improve graphene processes,
substrates such as glass,silicon,quartz,silicon oxide,sapphire and boron nitride were used for
graphene synthesis.CVD can produce high quality graphene with low defects,highly
interconnected
structure and large surface area.It has disadvantages such as high production cost,low
throughput,further purification to remove residue catalyst and transfer of graphene to other
substrates.

7. Epitaxial growth:

Graphene can also be prepared by thermal decomposition (1200-1600oC) of hexagonal substrate

(silicon carbide(SiC)) under vacuum or inert condition.High temperature causes silicon to
sublimate (Si melting point = 1100oC),leaving excessive C atoms to aggregate and form an sp2
hybridized network which include graphene growth.This process is known as epitaxial growth of
graphene on SiC.The graphene produced by this method lacks homogeneity.Epitaxial growth of
graphene would be expensive due to the energy intensive process and limited size of commercial
SiC substrate.Epitaxial growth can produce different polar faces such as Si-face or C-face which
hinder the graphene product quality.Using this method,the number of layers of graphene which
depends on heating temperature can be easily modulated.

8. Substrate-free gas-phase(SFGP):

SFGP is a relatively new method for synthesis of graphene material through gas phase reaction
without the presence of any substrates.An aerosol mixture of liquid ethanol and Ar is transferred
to a microwave-generated plasma at atmospheric condition.Graphene is formed when the ethanol
droplets are vaporized and dissociated in the plasma region over a timescale of 1s.It was found
that isopropyl alcohol and dimethyl ether precursors could yield graphene nanosheet.This method
has a high potential for scaling to commercial level as it can produce clean and high quality
graphene.

9. Template route:

The template method involved CVD template growth starting with physical vapor deposition
(PVD) to produce ZnS ribbon as the template for graphene growth with CH4 as the carbon
source.The residue ZnS nanobelt was etched with HCL.Another template route for graphene
synthesis is the self-assembly of graphene on a lamellar meso-structured silica template as the
carbon source which was derived from a pyrrole moiety-containing surfactant.This method was
highly controllable and gave high yield of graphene under mild operating conditions and
produced high quality and stable single-layer graphene with 0.6 nmthickness using non-
hazardous reagents.A soft-hard template method replaced the carbon source with cetyl trimethyl
ammonium bromide (CTAB) and tetramethoxysilane (TMOS) to form a sandwich-like
SiO2/CTAB/pyrene with CTAB as the soft template and SiO2 as the hard template.This method
is less desirable due
to the tedious washing step and the potential in destroying the produced graphene permanently
during template removal.

10. Total organic synthesis:

In total organic synthesis,graphene is fabricated based on the unique properties of polycyclic

aromatic hydrocarbons (PAHs).PAHs are often described as 2D graphene segment composed of
all sp2 carbons due to their structural size which is between molecular and macromolecular
phases.PAHs can be easily modified with suitable aliphatic chains to tailor the product
solubility.The key step of this process is to select suitable precursors to deliver high yield and
quality graphene via a simple reaction route,The quality of graphene might be affected by the
limited size range of PAHs which would decrease the graphene solubility and formation of side
reactions resulting from increased molecular weight.This method showed good progress in
graphene synthesis, but the occurence of side reactions and precise parametric control have
hindred its commercial application.

FEED STOCKS FOR GRAPHENE SYNTHESIS

The type of feed-stock would greatly affect the economic feasibility of graphene (and its
derivatives) synthesis as its mass production would require continuous supply of the carbon
precursor [40]. Graphite is the common source for the graphene synthesis.The grade of graphite
is dependent on its flake size and carbon content.Apart from graphite feed-stock, biomass
materials were studied as the feed-stock for oxidative exfoliation instead of graphite, and asphalt
was explored as the starting material in arc discharge synthesis to reduce the overall production
cost of graphene[].Biomass feed-stock such as wood, leaf, bagasse, fruit, newspaper, bone and
cow dung have been used to replace high quality graphite which is commonly used in oxidative
exfoliation- reduction process [136].Chemical vapour depotion utilizes fossil-based hydrocarbon
products such as benzene (C6H6), xylene (C8H10), toluene (C7H8 ), methanol (CH3OH) and
ethanol (C2 H5OH) for graphene synthesis [1377].
Food and animal wastes were used to replace fossil-based hydrocarbons to minimize cost and
eliminate usage of toxic raw materials[].plastic waste as a carbon source can be an alternative
way to reduce the waste and provide low cost feedstock for graphene.As observed, various
precursors are readily available from nature and industrial wastes which could significantly
reduce the production cost.

Fig no.3.Carbon precursors for synthesis of graphene and its derivatives

Potential industrial implementation of graphene synthesis methods

Each method produce the graphene with specified characteristics and the cost,scalibility depends
on the process parameters.Here we cover three important aspects applied as the primary
indicators in process evaluation,namely environment, economic and social indicators.The
environmental indicator on the use of resources (such as energy, material, water and land) and
the impacts on the environment (such as atmospheric, aquatic and land) due to emissions,
effluents and wastes generated by the process. The economic indicators cover the profit gained,
value-added and taxes paid, and investment made while the social indicators consider the
employment situation, health and safety at work, and impacts to the society [].

Based on the IChemE guidelines, six key indicators were identified for the present assessment on
the graphene synthesis methods, and these are: (i) cost (precursor cost and operating cost), (ii)
scalability potential, (iii) product quality, (iv) process condition (process safety and complexity),
(v) yield and (vi) environment (use of hazardous chemicals). The results are illustrated by the
radar charts in Fig. [].Radar chart is used here for representing the multi-varial.(0-for none,1-
low,2-average,3-high).The best method was identified based on the highest total score.

Fig[] each synthesis method had different characteristics in terms of cost, scalability, product
quality, process condition, yield and environment indicators. Mechanical exfoliation has been
reported to be inexpensive due to its simple operation and low cost feed-stock requirement such
as graphite[].How- ever, this synthesis route is considered labor intensive for production of
single-layer graphene and its yield is very low which may increase the overall operating cost
.The chance of getting impurities is very less compare to the other synthesis methods.As such,
this method was rated by an average score in cost, process condition and prod- uct quality and a
low score in scalability and yield in fig[].

Total organic synthesis is highly versatile in producing high yield graphene, but it has several
constraints which hinder its upscaling. In particular, precision control and extensive reaction
steps contributed to the low preference score in cost and pro- cess condition. Irregular shape and
defects led the total organic synthesis to the low preference score in product quality, process
condition and environment in fig[]

Template route has a low preference score in cost, scalability, product quality and process
condition due destruction at the purification step.The graphene quality produced through the
unzipping of CNT route is highly dependent on the type of CNT .Using of relatively expensive
feed-stock such as CNT is unfavorable in large-scale graphene production[].Plasma operation in
arc discharge method requires high voltages in delivering high temperature process condition to
size graphene. This has raised process safety concerns and incurred higher operating cost
compared to other synthesis methods as reflected by the low preference score for process
condition and cost in Fig.[].The number of graphene layer formed was hard to control, thus
limiting the potential industrial production of high quality graphene.
The potential application of epitaxial growth in industry is generally limited by the strict
operating conditions and the use of special equipment such as high temperature, ultrahigh
vacuum, inert condition and utilization of single-crystal substrate []. These have resulted in the
low preference score for commercialization in terms of cost, scalability, process condition and
yield .

The total score for oxidative exfoliation- reduction (16 points),CVD (13 points),and LPE (16
points).oxidative exfoliation-reduction, CVD and LPE have high potential for industrial
implementation.LPE has good potential for commercialization. The use of cheap feed-stock,
straightforward operation and use of environmentally friendly chemicals are the main
advantages of LPE which support its potential industrial implementation.The graphene produced
by LPE has lesser structural defects, thus many applications such as biosensors, energy storage
and functional devices employed this technique to produce graphene.
 Fig.5 .
Process evaluation of graphene synthesis: (a) mechanical exfoliation, (b) SFGP, (c) total organic synthesis,
(d) template route, (e) unzipping of CNT, (f) arc discharge, (g) epitaxial growth, (h) oxidative exfoliation-
reduction, (i) CVD and (j) LPE .
 PARAMETERS EFFECT

Role of anions on graphene production:

The easy access of sulfate anion into the graphite layer facilitates the diffusion of water
molecules into the bulk of the graphite during the anodic process, and the subsequent water
oxidation enables efficient exfoliation of graphite into graphene.Sulfate anion has the highest
repulsive binding energy to graphene layer compared to other anions,allowing reversible inter-
calation behavior into graphite51 .Sulfate-containing electrolytes, such as H2SO4, (NH4)2SO4 and
K2SO4, showed high exfoliation efficiency compared to other aqueous electrolyte systems.

Fig.6. The corresponding binding energies of the four anions

Optimized value of 1M H2SO4 yields high production rate and high quality graphene.511M
H2So4 higher production rate of 9.55mg/min and H3Po4 with least 0.84 mg/min51.Major
graphene are bi- layers H2SO4 for with thickness 1.5nm.Li+ diameter is 0.118nm and graphite
interlayer space is
0.335 nm hence the Li+ is not cause much exfoliation.Tetraethyl-ammonium cation TEA+ have
diameter 0.67 nm result in effective exfoliation51.

Role of voltage applied on graphene production

The quality of graphene and defects varies with the applied voltage while in electrochemical
exfoliation of graphene.GO samples produced at different synthesis voltages of 3, 5, 7, 10, 12,
and
14 V, respectively.Below 5 V, a thick and non-exfoliated GO sheets was observed. This
observation shows that the production of GO with thin and transparent sheets cannot be started at
or below than 3 V of synthesis voltage due to insufficient energy to exfoliate the bulk
graphite53.once the higher voltage was applied in the range of 7 to 12 V, the structures of GO
synthesized showed the crinkled silk-like sheets37,53.

Fig.no 7 defects at different voltage applied53

Id/Ig ratio increases with voltage (0.5 at 3v and 0.86 at 14v) so with increase in the applied
voltage increases the defects in the produced graphene.when the applied voltage increased, the
the tensile strees increased from 0.1973–0.4176 MPa and Young Modulus (E) increase from
2490– 20,200 MPa.High electrical conductivity observed at 7 v (4×10^-8 s/cm).7–14 V produced
graphene were burnt up at around 400 C (10–20 wt%) loss. The formation of multilayers
increases due to the increasing oxidation level(1–107 nm)53.
Role of sonication time on the graphene production
ultrasonic waves is important external factors with direct effects on fabricated graphene using
electrochemical exfoliation method.Applying ultrasonic waves to homogenize the electrolyte
decreases oxygen groups rate in graphene.It was also observed that the defects in the exfoliated
graphene sheets decreased with an increase the sonication time.H 2SO4 electrolyte with 45 min
sonication time had the highest stability, best electrical ,conductivity, lowest crystallite size,
fewer defects and lowest interlayer distance14.

Fig.no.8 Effect of electrolyte and sonication time on graphene product

Role of type solvent on graphene

The exfoliated powder then sonicated under two different solvents, which are
Dimethylformamide (DMF) and aqueous solution to form graphene. It was found that similar
structure of graphene was obtained from both types of solvent. However, the amount of graphene
produced was different due to the differences in graphene stability. Graphene is more stable in
DMF solvents compared to the aqueous solution. The aqueous solution can allow the reversible
reaction that can reform graphite oxide from graphene due to the existence of hydroxyl
component in the aqueous solution29.

Role of different organic solvents(DMSO,DMC/EC,NMP) on graphene

In this part compares the efficiency of electrochemical graphite exfoliation in dimethyl sulfoxide
(DMSO), N-methylpyrrolidone (NMP) and in a mixture of dimethyl carbonate (DMC) and
ethylene carbonate (EC) in an electrolyte consisting of LiClO4 and tetraethylammonium
tetrafluoroborate. This approach is useful in terms of the reduction in processing time and cost, as
well as aiding the control of the aggregation of graphene sheets.The formation of solid layer
electrolyte interface in the DMC/EC system is believed to stabilise the graphite from premature
exfoliation and allowed the ions to intercalate efficiently to produce a relatively high yield of
monolayer graphene sheets4

Fig.no9.comparing different solvents

By contrast, the electrochemical exfoliation of graphite in the other two solvents (DMSO and
NMP) produced lower yields of few layer graphene.DMC/EC yields high compared to NMP and
DMSO,so DMC is most preferable for large scale production.The graphite exfoliation not much
observed in DMC solvent and NMP 4..0.04 mg/ml concentration obtained from Li in DMC/EC
high yield compared to NMP and DMSO.Ratio of D/G of DMC/EC ,DMSO,and NMP was
1.4,0.65,0.3.Li+ and TEA+ with 1:1 volume mixture in DMC/EC was optimum electrolyte4,13.

Role of different inorganic solvents on graphene

The graphene prepared using (NH4)2HPO4electrolyte showed the lowest level of defects in
comparison to the other.The Id/Ig changes depending on the salt used, with the amount of
disorder increasing as (NH4)2HPO4<(NH4)2SO4<Na2SO4<NH4NO3.Addition of even a low
concentration of (NH4)2HPO4 to (NH4)2SO4 the electrolyte can prevent excessive oxidation.
 Fig.no.10 number of layers and fraction yield of graphene

Fig.no.12 conductivity vs inorganic solvents

Role of Temperature affect on different inorganic electrolytes

The method is based on graphene exfoliation in inorganic electrolytes (e.g. (NH4)2HPO4 and
(NH4)2SO4 and different combinations of these salts) where the electrolyte composition was
found to have a significant impact on the yield, morphology, structure, and high-temperature
stability of the graphene sheets. The graphene prepared using (NH4)2HPO4 electrolyte showed
the lowest level of defects in comparison to the other electrochemically exfoliated graphene and
an exceptional high-temperature stability in air, at temperatures of up to 750 °C
 Fig13.weight loss of different electrolyte on temperature

This clearly shows that graphene produced with (NH4)2HPO4 has a high-temperature stability
compared to the other.phosphorous containing functional groups can enhance high-temperature
stability of carbon materials.(up to 8500c).