SYNTHESIS, CHARACTERIZATION AND

APPLICATION OF GRAPHENE
BY ELECTROCHEMICAL METHOD

GROUP MEMBERS PROJECT ADVISOR:

KANWAL ZEHRA (MM-014)
DR. ALI DAD CHANDIO
FAZILA NOOR (MM-026)
AROOBA RASHEED (MM-301)
 OUTLINE
• Introduction and importance of electrochemical process
• Review of article
• Innovations
• Voltage variation
• Electrolyte variation
• Sonication variation
• Centrifuge (rpm) Variation
• Electrical testing Comparison
• Characterization
• SEM
• AFM
• XRD
• UV
• FTIR
• Stereo microscopy
• Application
• Future work
• References
INTRODUCTION
SYNTHESIS OF GRAPHENE

Dispersed graphene
Oven treatment
 COMPARISON WITH OTHER
METHODS
CVD HUMMER’S METHOD
• CVD methods growing • Drawn much attention due to:
large-area graphene, • The advantages of potentially
low-cost and solution-
• Should be made to processed fabrication.
lower the production • Oxidation process damages
costs, the honeycomb lattices of
graphene.
• Particularly those
associated with the • Reduction of go involves high
high-temperature temperature to recover the
graphitic structure.
process and expensive
substrates.
EXFOLIATION METHODS
• 1. Liquid-phase exfoliation of
graphite by extended
sonication and 2. Intercalation
and expansionof graphite with
volatile agents
• The high resistance of these TC
films is caused by the damage
during exfoliation
• Large amounts of intersheet
junctions.
 IMPORTANCE OF ELECTROCHEMICAL
PROCESS
• Provide a continuous layer
• Directly applicable product
• Flexible
• Transparent (96%)
• After annealing gives good
conductivity
 APPLICATIONS

Mechanical Thermal

Nano Technology
Optical and Electrical 7
REVIEW OF ARTICLE
 REVIEW OF ARTICLE CONT.
ELECTRODES:
Cathode: Pure Platinum wire
Anode: Expanded graphite

ELECTROLYTE:
SULPHURIC ACID(4.8 ml) + DEIONIZE
WATER(100ml)

DC POWER: 1VOLT (30 MINUTES)

10 VOLTS (5 MINUTES)

SONICATION TIME: 5 MINUTES

CENTRIFUGE: 2500 RPM (20 MINUTES) in

DIMETHYLE FORMAMIDE(DMF)
 EXPANDABLE GRAPHITE

PREPARATION OF EXPANDED GRAPHITE BY HYDROTHERMAL METHOD [1]

1. H2SO4 (20 ml)+HNO3 (5 ml)+graphite powder (5 gm)

2. Mixed by magnetic stirrer (30 min.) in ice bath
3. Teflon-lined Autoclaved for 2 hour (180°C)
4. Filtered and neutralized
5. Left for 24 hours Stirring in ice bath

6. Oven treat at 180°C for 2 hours

Autoclave
7. Furnace heat at 1000°C for 30 sec
8. Weight of electrode (10 gm)

Neutralized powder
GRAPHITE NANOPLATELETS(GNPs)

Particles floating over water

 SCANNING ELECTRON
MICROSCOPY OF (GNPs)[3]

GNPs

160x

400x
10,000x

Performed
Reported
400x
 GRAPHITE NANOPLATELETS(GNPs)
• GNPs can be made by hydrothermal process
• After neutralizing (step 4) GNPs can be collected
• Resistance found (13 - 45)kΩ
 REVIEW OF ARTICLE CONT.

Electrolysis: 1V 30 min Drying: (20-24 hours) at RT Sonicate: 5 min

Filtration
10 V 1 min.

Dispersed graphene
Centrifuge: 2500 rpm in DMF Oven heat: 190°C Electrical testing: 116.5 kΩ
 CHANGING IN PARAMETERS
Electrode And Voltage Variation
 ELECTRODES: Pure graphite electrodes
(cathode & anode)

ELECTROLYTE: H2SO4
(4.8ml) + DI H2O (100 ml)

ELECTROLYSIS: 1 volt: 10 min., 10 volts: 10

min., 10 V-30 min.

Sonicate : 5 min.

Centrifuge : 2500 rpm

Oven heat : 190°C , 30 min.

 COMPARISON OF GRAPHITE
ELECTRODES
Porous graphite Compact graphite

• Pure graphite electrodes • Highly pure graphite

• Obtained from Electric Arc Furnace electrode • Obtained from Potentiostat
• Electrode Resistance found: 3Ω • Electrode Resistance found: (1-2)Ω
• More yield(exfoliation) and low resistance(Ω-kΩ) • Less yield (exfoliation) and
comparable resistance(kΩ-MΩ)
 COMPACT ELECTRODE AND
VOLTAGE VARIATION

Electrolysis: 1V 10 min Drying: (20-24 hours) Sonicate: 5 min

Filtration
10 V 5 min.

Dispersed graphene
Centrifuge: 2500 rpm in DMF Oven heat: 190°C Electrical testing: 116.5 kΩ
 RESULT OF VOLTAGE VARIATION
CYCLE 1
1volt: 30 min. ; 10 volt: 5min.
CYCLE 2
1 volt: 10 min. ;10 volt: 10 min
CYCLE 3
1 volt: 5 min. ; 10 volt: 15 min

• Better yield without making expandable

• Linear relation found between voltage exposure(10-12 volts) and
yield (exfoliation)
• Resistance readings comparable with reported (0.043-191)kΩ

Problems
• More high voltages gives more coarser particles exfoliate, not
preferable
• At high voltages graphite gives burned particle, effect properties
CHANGING IN PARAMETERS
Electrolyte Variation
 ELECTRODES: Pure graphite Electrolyte Variation
electrodes (cathode &
anode)

ELECTROLYTE: H2SO4 (6 ml) or KOH

(11 ml) + DI H2O (150 ml)

ELECTROLYSIS: 1 volt: 10
min., 10volts: 10 min.

Sonicate : 5 min.

Centrifuge : 2500 rpm

Oven heat : 190°C, 30 min.

 ELECTROLYTE VARIATION CONT.
RESULTS
Cycle 1
H2SO4 (9.6 ml) + Deionize water (100ml) (14-62)kΩ
Cycle 2
H2SO4 (6 ml) + Deionize water (150ml) (0.26-192)kΩ
Cycle 3
H2SO4 (2.4 ml) + Deionize water (150ml) + KOH (11ml) (1.5-40)MΩ
Cycle 4
H2SO4 (0.4 ml) + Deionize water (100ml) + KOH (13ml) (0.063-0.878)MΩ
 ELECTROLYTE VARIATION CONT.
RESULTS
• Increasing quantity of H2SO4 in electrolyte oxidizes graphene hence
increase resistance
• Addition of KOH(weak base) and decrement of H2SO4 (strong acid)
decreases in electrolyte the exfoliation rate by decreasing the grain
boundary weakening of graphite layers.
• First cycle is preferable
CHANGING IN PARAMETERS
Sonication Time and chemical
variation
 Sonication time
ELECTRODES: Pure graphite & chemical
electrodes (cathode & anode)
Variation
ELECTROLYTE: H2SO4
(4.8ml) + DI H2O (100 ml)

ELECTROLYSIS: 1 volt: 10 min.,

10 volts: 10 min.

Sonicate : 5 min., 10 min & 30 min

Chemical : Acetone and DMF

Centrifuge : 2500 rpm

Oven heat : 190°C, 30 min.

 SONICATION TIME & CHEMICAL
VARIATION CONT.
• Dispersing chemical for sonication
• Acetone (2.3 -15.5)MΩ
• Dimethyle Formamide (DMF) (37 - 65)kΩ
• Sonication time
• 5 minutes
• 10 minutes (0.7-175)kΩ
• 30 minutes
 SONICATION TIME & CHEMICAL
VARIATION CONT.
Dispersing chemical for sonication
• Acetone and DMF act as surfactant
• DMF results in low resistance relative to the Acetone
• DMF segregate the graphene particles more than Acetone
Sonication time
Increasing the sonication time not affects the resistance value much
CHANGING IN PARAMETERS
Centrifuge (rpm) & time
variation
 ELECTRODES: Pure graphite
Centrifuge (rpm)
electrodes (cathode & anode)
Variation
ELECTROLYTE: H2SO4 (6 ml) or KOH
(11 ml) + DI H2O (150 ml)

ELECTROLYSIS: 1 volt: 10 min.,

10volts: 10 min.

Sonicate : 5 min.

Centrifuge : 2500 rpm, 3000 pm & 4000 rpm

Time: 20, 30 min

Oven heat : 190°C, 30 min

 CENTRIFUGE (RPM) AND TIME
VARIATION CONT.
• Rpm
• At 2500: ( 0.26 – 192) kΩ
• At 3000: (0.08 – 1.176)kΩ
• At 4000: 18Ω – 0.378kΩ

• Time variation
• 20 min (14 - 62)kΩ
• 30 min (0.043 - 191)kΩ
 CENTRIFUGE (RPM) AND TIME
VARIATION CONT.
Rpm
• Increasing the rpm decreases the resistance
• More rpm give finer particles of graphene, decrease the resistance

Time variation
• Inverse relation found between time and rpm
• At higher rpms and less time decrease resistance
• At lower rpms and more time also decrease resistance
 COMPARISON W.R.T. ELECTRICAL TESTING
VARIATIONS OBSERVED IN RESISTANCE
TESTING (Ω)
VOLTAGE [ yield (0.3-0.9)gm] (0.043-191)kΩ

0.26kΩ-40MΩ
ELECTROLYTE

SONICATION (0.7-175) kΩ

Rpm of centrifuge: 18 Ω-0.378kΩ

 CONCLUSION

Voltage variation Centrifuge (rpm)

• Exposure at low voltages for long • low rpms for long time can provide
hours can give highly fine particles good results of conductivity
of graphene.
• Hence, increased conductivity.
CHARACTERIZATION
 ATOMIC FORCE
MICROSCOPY(AFM)
Thickness:
114nm-8µm
Reported [2] Sheet Performed

Flakes
Sheet thickness: 1.49 nm
 SCANNING ELECTRON MICROSCOPY
(SEM)
Reported [4,5] Performed
Flakes
80x

2.941 µm to 23.529 µm

3000x 12,000x
 X-RAY DIFFRACTION (XRD)

Reported [6] Performed

Max. hump
at 2ѳ=26.6°
 FOURIER TRANSFORM-INFRARED(FT-IR)

Reported [2] Performed

Transmittance (%)
180

160

140

120

100

80 O-C
O-H
60 O-C
40

20 C=C
0
0 500 1000 1500 2000 2500 3000

1657 cm-1
 UV-SPECTROSCOPY

Reported [6] Performed

[%]Transmittance
250

200

150

100

50

0
260 262 264 266 268 270 272

-50

266 nm
 STEREO MICROSCOPY
Few layer Graphene
sheets, 16x
Reported [2] Performed

Optical image of the cast thin-conducting

electrodes on quartz substrates. Graphite Magnification: 35x
APPLICATION
DI-SYNTHESIZED SOLAR CELL (DSSC)
 REQUIREMENTS OF DSSC
• Two Electrodes required
• Photo anode (TiO2 coated glass )
• Counter electrode (Graphene coated glass)
• Placement of spacer between electrodes (plastic sheet)
• Drop by drop added Potassium Iodide (60wt% KI) as electrolyte
• Placed in solar energy
• Electrical test
 MAKING OF DI-SYNTHESIZED SOLAR CELL (DSSC).
PREPARATION OF PHOTO ANODE

• TiO2 powder (5 gm.)

• Ethanol (30 ml)
• Acetic acid (10 ml)
• De-ionize water (5
ml)

Mixing of constituents Heated at 200°C for 30

Precursors Slurry applied on ITO
(30 minutes) min.
coated by rolling method.

Dip in pomegranate liquid (30 min.) Dry in dark box for 30 min.
 SOLAR TESTING
Counter electrode Stickled electrodes
• Graphene layer coated upon
(3*3)cm2 glass substrate

RESULT
Voltage obtained: 0.388 Volts
 FUTURE WORK

Recommended
• Acid treatment, dip in HNO3 heat at 80°C
• Treatment in tube furnace (450°C for 30
min)
• Under H2/Argon environment
can increase conductivity
 REFERENCES

• [1]Tsai, K.-C., et al., Preparation of expandable graphite using a hydrothermal method and
flame-retardant properties of its halogen-free flame-retardant HDPE composites. Journal of
Polymer Research, 2011. 18(4): p. 483-488.
• [2].https://www.google.com.pk/url?sa=t&rct=j&q=&esrc=s&source=web&cd=1&cad=rja&ua
ct=8&ved=0ahUKEwj4qNDysofQAhXDfxoKHRvVD6EQFgggMAA&url=http%3A%2F%2Fwww.nt
mdt.com%2Fdata%2Fmedia%2Ffiles%2Fpublications%2Fdb%2FACSNano_graphene_Su_Ram
an.pdf&usg=AFQjCNHyzmLZuRQ5DdA-LpJ_T4988Rn8vg&bvm=bv.137132246,d.bGs
• [3] http://news.rice.edu/2016/09/02/3-d-graphene-has-
promisehttp://news.rice.edu/2016/09/02/3-d-graphene-has-promise-for-bio-applications/-
for-bio-applications/
• [4] https://www.hielscher.com/ultrasonic-graphene-preparation.htm
• [5]https://www.google.com.pk/search?rlz=1C1CHWL_enPK673PK674&biw=1517&bih=654&n
oj=1&tbm=isch&sa=1&q=graphite+nano+platelets+sem+images&oq=graphite+nano+platel
ets+sem+images&gs_l=img.3...76041.77774.0.78564.6.6.0.0.0.0.188.557.0j3.3.0....0...1c.1.64.img.
.3.0.0.iZDU06ZEWaM#imgrc=Rk-lLrLByeSZRM%3A
• [6] http://www.sciencedirect.com/science/article/pii/S1385894711016263
Thank you