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Analysis of Co3O4@ x % rGO (x =0%,5%,10%,15%) as Effective Electrode Material
in Supercapacitors
Presented By : Jahanzaib Mughal
Roll No: CSSP-R41-F21
Session: 2021-23
Supervised by : Dr.Shahid Atiq
CENTER OF EXCELLENCE IN SOLID STATE PHYSICS,
UNIVERSITY OF THE PUNJAB,
LAHORE (QAC)
Center of excellence
in solid state physics
Super + capacitor
9/14/2023 1
 Higher Energy Density
 Higher Power Density
 Higher Capacity
 Longer Life
9/14/2023 2
Things that makes a
capacitor, super
Properties Capacitor Supercapacitor Battery
Energy density
(Wh/kg)
˂0.1 1-10 10-100
Power density
(W/kg)
>1,000,000 10,000 1000
Discharging time
(sec)
10-3 – 10-6 1-30 >0.3 h
Charging time (sec) 10-3 – 10-6 1-30 1˂t>5 h
Cyclic stability 106 106 1,000
Materials Science and Engineering. 561. 012105. 10.1088/1757-899X/561/1/012105.
9/14/2023 3
Comparison between different
energy storage devices
9/14/2023 4
What is Supercapacitor ?
Current collectors
An energy storage device having capacitance in
between 100F to 5kF with higher power density and
cyclic life than batteries and higher energy density than
conventional capacitors, is called Ultracapacitor or
Supercapacitor.
Based on the charge storage mechanism, it can be
classified in 2 basic types
• Electric double layer capacitors
• Pseudo capacitors
9/14/2023 5
Charge Storage
Mechanism
Electro Static
Charge Storage
Mechanism
Electro Dynamic
Charge Storage
Mechanism
Electric + Hodos
Charge + way/ path
Conductors that are used to make electric contacts with non-metallic
part of the circuit
Type
(-ve charge) Cathod Anode (+ve charge)
Electrodes
9/14/2023 6
9/14/2023 7
Most Preferred Electrode
materials
Motivation behind
Ideal electrode
• Conductive
• Maximal surface area
• Mechanical stability
• Clear and sharp melting
temperatures
• Minimal internal resistance
• Appropriate electrolyte interaction
• Good specific capacitance
Co3O4
.
.
.
.
.
.
.
9/14/2023 8
9/14/2023 9
Literature Review
Electrode Fabrication
Graphical abstract
9/14/2023 10
Hydrothermal Synthesis Route
Co(NO3)2 + DI water C₂H₆O₂
HNO3
autoclave
Teflon container
Centrifuge washing
Muffle furnace
4h at 140º
oven
Mortar & pestle
Box furnace
2h at 550º
Co3O4
nano particles
Preparation of Active Material by Solvothermal Method
Aqueous Solution
Ultrasonic Bath Stirring Teflon Box & Autoclave
Muffle Furnace
Centrifuge
Heating
Active Mass
Co3O4 + x % rGO + Ethanol Sonification for 40 mints Stirring for 4 hours
Aqueous Solution in
autoclave
Constant heating at
60℃ 𝐟𝐨𝐫 𝟐 𝐡𝐨𝐮𝐫𝐬
Kept for 5
hours at 140 ℃
Washing
9/14/2023 12
Preparation of Slurry
Active Mass 85%
Binder 10%
Activated Carbon 5%
Stirring For 8 hours
Slurry
9/14/2023 13
PVDF + DMF
50ml Etching
Solution
Ni Foam Ni Foam dipped in
Etching Solution
Ultrasonic Bath
Oven
Oven
Prepared Electrode
13ml of HCL 37ml of DI Water
Cutting of Ni Foam
of Size 1× 𝟏 (𝐜𝐦)
Sonification Etching Sol.
Ni Foam kept for
20 Mints
drying for 20 Mints
Coating on Ni
Foam
Coating of slurry
Preparation of Electrode
9/14/2023 14
X-ray Diffraction
For structural conformations
9/14/2023 15
Equinox 2000,
Thermo Fisher Scientific USA
9/14/2023 16
Characterization
Apparatus
10 20 30 40 50 60 70 80
¨
¨
Co3O4 +10% rGO
Co3O4 +5% rGO
Co3O4 + 0% rGO
Intensity
(Arb.
units)
2q
(
Degree)
Co3O4 +15% rGO
©
©
© Ni (foam)
ICSD card # 00-004-0850
¨
¨
¨
¨
¨
¨
¨ Co2O4
ICSD card # 00-042-1467
©
9/14/2023 17
XRD Pattern
• Calculated parameters
α=β=γ=90°
a=b=c=8.065 Å
Cubic structure
Cell volume 524.5 Å3
• ICSD card parameters
α=β=γ=90°
a=b=c=8.083 Å
Cubic structure
Cell volume 528.54 Å3
9/14/2023 18
Comparison of
Lattice Parameters
• The portion of crystal which diffracts the light coherently, is know as
crystallite size
𝑫 =
𝒌𝝀
𝜷𝒄𝒐𝒔𝜽
k is the shape factor having a constant value of 0.9.
9/14/2023 19
Crystallite size
9/14/2023 20
Variation in
Crystallite size
0 5 10 15
0
5
10
15
20
25
30
35
40
Crystalite
size
(nm)
rGO Composition (%)
Crystalite size of Co3O4 @ x % rGO
25.43 nm
24.49 nm 24.19 nm 24.00 nm
Cyclic Voltammetry
To observe the redox reaction route
OGS 2000 Origalys Potentiostate
9/14/2023 22
Characterization
Apparatus
0.0 0.1 0.2 0.3 0.4
-0.04
-0.02
0.00
0.02
0.04
0.06
Current
(A)
Potential (V)
5mV/s
10mV/s
20mV/s
30mV/s
50mV/s
100mV/s
Co3O4 @ 0% rGO
(a)
0.0 0.1 0.2 0.3 0.4
-0.04
-0.02
0.00
0.02
0.04
0.06
Current
(A)
Potential (V)
5mV/s
10mV/s
20mV/s
30mV/s
50mV/s
100mV/s
Co3O4 @ 5% rGO
(a)
CV curves in 2M KOH electrolyte with (a) Co3O4 @ 0% rGO (b) Co3O4 @ 5% rGO
9/14/2023 23
CV curves
9/14/2023 24
0.0 0.1 0.2 0.3 0.4
-0.04
-0.02
0.00
0.02
0.04
0.06
Current
(A)
Potential (V)
5mV/s
10mV/s
20mV/s
30mV/s
50mV/s
100mV/s
Co3O4 @ 10% rGO
(c)
0.0 0.1 0.2 0.3 0.4
-0.04
-0.02
0.00
0.02
0.04
0.06
Current
(A)
Potential (V)
5mV/s
10mV/s
20mV/s
30mV/s
50mV/s
100mV/s
Co3O4 @ 15% rGO
(b)
CV curves in 2M KOH electrolyte (c) Co3O4 @ 10% rGO (d) Co3O4 @ 15% rGO
CV curves
Galvanostatic Charge-Discharge
Measurements
For performance of energy storage devices
Galvano-state Impedance meter,
Origa Stat OGS 2000
9/14/2023 26
Characterization
Apparatus
9/14/2023 27
0 50 100 150 200 250 300
0.0
0.1
0.2
0.3
0.4
Potential
(V)
Time (sec)
1A/g
2A/g
3A/g
4A/g
Co3O4 + 0% rGO
(a)
-100 0 100 200 300 400 500 600 700
0.0
0.1
0.2
0.3
0.4
Potential
(V)
Time (sec)
1A/g
2A/g
3A/g
4A/g
Co3O4 + 5% rGO
(b)
GCD curves in 2M KOH electrolyte with (a) Co3O4 @ 0% rGO (b) Co3O4 @ 5% rGO
GCD Curves
9/14/2023 28
0 100 200 300 400 500 600 700
0.0
0.1
0.2
0.3
0.4
Potential
(V)
Time (sec)
1A/g
2A/g
3A/g
4A/g
Co3O4 + 10% rGO
(c)
-100 0 100 200 300 400 500 600 700 800
0.0
0.1
0.2
0.3
0.4
Potential
(V)
Time (sec)
1A/g
2A/g
3A/g
4A/g
Co3O4 + 15% rGO
(d)
GCD curves in 2M KOH electrolyte with (c) Co3O4 @ 10% rGO (d) Co3O4 @ 15% rGO
GCD Curves
Sample 1A/g 2A/g 3A/g 4A/g
Discharge
time (sec)
Specific
capacitance
(F/g)
Discharge
time (sec)
Specific
capacitance
(F/g)
Discharge
time (sec)
Specific
capacitanc
e (F/g)
Discharge
time (sec)
Specific
capacitance (F/g)
Co3O4 @0% rGO 132.882 332.205 46.359 231.795 22.651 169.882
5
7.7 77
Co3O4 @5% rGO 275.795 689.4875 86.206 431.03 27.126 203.445 6.318 63.18
Co3O4 @10% rGO 296.527 741.3175 125.918 629.598 29.933 299.497
5
9.521 95.21
Co3O4 @15% rGO 320.888 802.22 122.455 612.275 59.315 444.862
5
21.123 211.23
9/14/2023 29
Specific Capacitance at Different Current Densities
9/14/2023 30
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
0
200
400
600
800
Specific
Capacitance
(F/g)
Current Density (A/g)
Co3O4 @ 0% rGO
Co3O4 @ 5% rGO
Co3O4 @ 10% rGO
Co3O4 @ 15% rGO
Trend of Specific Capacitance with increasing Current Densities along with the error correction
Specific Capacitance Vs
Current Density
9/14/2023 31
0.2 0.3 0.4 0.5 0.6 0.7 0.8
0
10
20
30
40
50
60
70
Energy
Density
Wh/kg
Power Density (W/kg)
Co3O4 @ 0% rGO
Co3O4 @ 5% rGO
Co3O4 @ 10% rGO
Co3O4 @ 15% rGO
Power Vs Energy Density
9/14/2023 32
Electroscopic Impedance
Spectroscopy
Capacitive & resistive behavior
9/14/2023 33
EIS Curves
2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0
-0.4
0.0
0.4
0.8
1.2
1.6
-Z"(W)
Z'(W)
Co3O4 @ 0% rGO
(a)
1.7 1.8 1.9 2.0 2.1
0.0
0.2
0.4
0.6
0.8
Z''
(W)
Z'(W)
Co3O4 @ 5% rGO
(c)
9/14/2023 34
EIS Curves
2.10 2.15 2.20 2.25 2.30 2.35 2.40
0.0
0.2
0.4
0.6
-Z"(W)
Z' (W)
Co3O4 @ 15% rGO
(d)
1.4 1.5 1.6 1.7
-0.2
0.0
0.2
0.4
0.6
0.8
-Z"(W)
Z'(W)
Co3O4 @ 10% rGO
(b)
• Highly pure crystalline cubic structures are confirmed by XRD with
average crystallite size of 24.4 Å
• CV curves confirms the pseudo capacitive behavior of Co3O4 @ x %
rGO composites
• Comparatively, better energy and power densities are observed of
Co3O4 @ 15% rGO composite along with longer discharging time
• An unexpected specific capacitance at 2A/g is observed with Co3O4
@ 10% rGO
9/14/2023 35
Conclusion
9/14/2023 36
Co3O4 @ 15% rGO composite
is preferable for practical device
fabrication at low current
densities
Remarks
9/14/2023 37
Acknowledgment
Center Of Excellence in Solid State Physics, PU
Department of physics, COMSATS University
US Pecas, NUST
DS&T, University of Education
Dr. Shahid Atiq
Mr.Umer Waqas
Mr. Amaar Tariq
Special Thanks
Suggestions
please
9/14/2023 38
Thank you
9/14/2023 39

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cobalt oxide composed with rGO as effective electrode material

  • 1. Analysis of Co3O4@ x % rGO (x =0%,5%,10%,15%) as Effective Electrode Material in Supercapacitors Presented By : Jahanzaib Mughal Roll No: CSSP-R41-F21 Session: 2021-23 Supervised by : Dr.Shahid Atiq CENTER OF EXCELLENCE IN SOLID STATE PHYSICS, UNIVERSITY OF THE PUNJAB, LAHORE (QAC) Center of excellence in solid state physics
  • 3.  Higher Energy Density  Higher Power Density  Higher Capacity  Longer Life 9/14/2023 2 Things that makes a capacitor, super
  • 4. Properties Capacitor Supercapacitor Battery Energy density (Wh/kg) ˂0.1 1-10 10-100 Power density (W/kg) >1,000,000 10,000 1000 Discharging time (sec) 10-3 – 10-6 1-30 >0.3 h Charging time (sec) 10-3 – 10-6 1-30 1˂t>5 h Cyclic stability 106 106 1,000 Materials Science and Engineering. 561. 012105. 10.1088/1757-899X/561/1/012105. 9/14/2023 3 Comparison between different energy storage devices
  • 5. 9/14/2023 4 What is Supercapacitor ? Current collectors An energy storage device having capacitance in between 100F to 5kF with higher power density and cyclic life than batteries and higher energy density than conventional capacitors, is called Ultracapacitor or Supercapacitor. Based on the charge storage mechanism, it can be classified in 2 basic types • Electric double layer capacitors • Pseudo capacitors
  • 6. 9/14/2023 5 Charge Storage Mechanism Electro Static Charge Storage Mechanism Electro Dynamic Charge Storage Mechanism
  • 7. Electric + Hodos Charge + way/ path Conductors that are used to make electric contacts with non-metallic part of the circuit Type (-ve charge) Cathod Anode (+ve charge) Electrodes 9/14/2023 6
  • 8. 9/14/2023 7 Most Preferred Electrode materials
  • 9. Motivation behind Ideal electrode • Conductive • Maximal surface area • Mechanical stability • Clear and sharp melting temperatures • Minimal internal resistance • Appropriate electrolyte interaction • Good specific capacitance Co3O4 . . . . . . . 9/14/2023 8
  • 12. Hydrothermal Synthesis Route Co(NO3)2 + DI water C₂H₆O₂ HNO3 autoclave Teflon container Centrifuge washing Muffle furnace 4h at 140º oven Mortar & pestle Box furnace 2h at 550º Co3O4 nano particles
  • 13. Preparation of Active Material by Solvothermal Method Aqueous Solution Ultrasonic Bath Stirring Teflon Box & Autoclave Muffle Furnace Centrifuge Heating Active Mass Co3O4 + x % rGO + Ethanol Sonification for 40 mints Stirring for 4 hours Aqueous Solution in autoclave Constant heating at 60℃ 𝐟𝐨𝐫 𝟐 𝐡𝐨𝐮𝐫𝐬 Kept for 5 hours at 140 ℃ Washing 9/14/2023 12
  • 14. Preparation of Slurry Active Mass 85% Binder 10% Activated Carbon 5% Stirring For 8 hours Slurry 9/14/2023 13 PVDF + DMF
  • 15. 50ml Etching Solution Ni Foam Ni Foam dipped in Etching Solution Ultrasonic Bath Oven Oven Prepared Electrode 13ml of HCL 37ml of DI Water Cutting of Ni Foam of Size 1× 𝟏 (𝐜𝐦) Sonification Etching Sol. Ni Foam kept for 20 Mints drying for 20 Mints Coating on Ni Foam Coating of slurry Preparation of Electrode 9/14/2023 14
  • 16. X-ray Diffraction For structural conformations 9/14/2023 15
  • 17. Equinox 2000, Thermo Fisher Scientific USA 9/14/2023 16 Characterization Apparatus
  • 18. 10 20 30 40 50 60 70 80 ¨ ¨ Co3O4 +10% rGO Co3O4 +5% rGO Co3O4 + 0% rGO Intensity (Arb. units) 2q ( Degree) Co3O4 +15% rGO © © © Ni (foam) ICSD card # 00-004-0850 ¨ ¨ ¨ ¨ ¨ ¨ ¨ Co2O4 ICSD card # 00-042-1467 © 9/14/2023 17 XRD Pattern
  • 19. • Calculated parameters α=β=γ=90° a=b=c=8.065 Å Cubic structure Cell volume 524.5 Å3 • ICSD card parameters α=β=γ=90° a=b=c=8.083 Å Cubic structure Cell volume 528.54 Å3 9/14/2023 18 Comparison of Lattice Parameters
  • 20. • The portion of crystal which diffracts the light coherently, is know as crystallite size 𝑫 = 𝒌𝝀 𝜷𝒄𝒐𝒔𝜽 k is the shape factor having a constant value of 0.9. 9/14/2023 19 Crystallite size
  • 21. 9/14/2023 20 Variation in Crystallite size 0 5 10 15 0 5 10 15 20 25 30 35 40 Crystalite size (nm) rGO Composition (%) Crystalite size of Co3O4 @ x % rGO 25.43 nm 24.49 nm 24.19 nm 24.00 nm
  • 22. Cyclic Voltammetry To observe the redox reaction route
  • 23. OGS 2000 Origalys Potentiostate 9/14/2023 22 Characterization Apparatus
  • 24. 0.0 0.1 0.2 0.3 0.4 -0.04 -0.02 0.00 0.02 0.04 0.06 Current (A) Potential (V) 5mV/s 10mV/s 20mV/s 30mV/s 50mV/s 100mV/s Co3O4 @ 0% rGO (a) 0.0 0.1 0.2 0.3 0.4 -0.04 -0.02 0.00 0.02 0.04 0.06 Current (A) Potential (V) 5mV/s 10mV/s 20mV/s 30mV/s 50mV/s 100mV/s Co3O4 @ 5% rGO (a) CV curves in 2M KOH electrolyte with (a) Co3O4 @ 0% rGO (b) Co3O4 @ 5% rGO 9/14/2023 23 CV curves
  • 25. 9/14/2023 24 0.0 0.1 0.2 0.3 0.4 -0.04 -0.02 0.00 0.02 0.04 0.06 Current (A) Potential (V) 5mV/s 10mV/s 20mV/s 30mV/s 50mV/s 100mV/s Co3O4 @ 10% rGO (c) 0.0 0.1 0.2 0.3 0.4 -0.04 -0.02 0.00 0.02 0.04 0.06 Current (A) Potential (V) 5mV/s 10mV/s 20mV/s 30mV/s 50mV/s 100mV/s Co3O4 @ 15% rGO (b) CV curves in 2M KOH electrolyte (c) Co3O4 @ 10% rGO (d) Co3O4 @ 15% rGO CV curves
  • 27. Galvano-state Impedance meter, Origa Stat OGS 2000 9/14/2023 26 Characterization Apparatus
  • 28. 9/14/2023 27 0 50 100 150 200 250 300 0.0 0.1 0.2 0.3 0.4 Potential (V) Time (sec) 1A/g 2A/g 3A/g 4A/g Co3O4 + 0% rGO (a) -100 0 100 200 300 400 500 600 700 0.0 0.1 0.2 0.3 0.4 Potential (V) Time (sec) 1A/g 2A/g 3A/g 4A/g Co3O4 + 5% rGO (b) GCD curves in 2M KOH electrolyte with (a) Co3O4 @ 0% rGO (b) Co3O4 @ 5% rGO GCD Curves
  • 29. 9/14/2023 28 0 100 200 300 400 500 600 700 0.0 0.1 0.2 0.3 0.4 Potential (V) Time (sec) 1A/g 2A/g 3A/g 4A/g Co3O4 + 10% rGO (c) -100 0 100 200 300 400 500 600 700 800 0.0 0.1 0.2 0.3 0.4 Potential (V) Time (sec) 1A/g 2A/g 3A/g 4A/g Co3O4 + 15% rGO (d) GCD curves in 2M KOH electrolyte with (c) Co3O4 @ 10% rGO (d) Co3O4 @ 15% rGO GCD Curves
  • 30. Sample 1A/g 2A/g 3A/g 4A/g Discharge time (sec) Specific capacitance (F/g) Discharge time (sec) Specific capacitance (F/g) Discharge time (sec) Specific capacitanc e (F/g) Discharge time (sec) Specific capacitance (F/g) Co3O4 @0% rGO 132.882 332.205 46.359 231.795 22.651 169.882 5 7.7 77 Co3O4 @5% rGO 275.795 689.4875 86.206 431.03 27.126 203.445 6.318 63.18 Co3O4 @10% rGO 296.527 741.3175 125.918 629.598 29.933 299.497 5 9.521 95.21 Co3O4 @15% rGO 320.888 802.22 122.455 612.275 59.315 444.862 5 21.123 211.23 9/14/2023 29 Specific Capacitance at Different Current Densities
  • 31. 9/14/2023 30 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 0 200 400 600 800 Specific Capacitance (F/g) Current Density (A/g) Co3O4 @ 0% rGO Co3O4 @ 5% rGO Co3O4 @ 10% rGO Co3O4 @ 15% rGO Trend of Specific Capacitance with increasing Current Densities along with the error correction Specific Capacitance Vs Current Density
  • 32. 9/14/2023 31 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0 10 20 30 40 50 60 70 Energy Density Wh/kg Power Density (W/kg) Co3O4 @ 0% rGO Co3O4 @ 5% rGO Co3O4 @ 10% rGO Co3O4 @ 15% rGO Power Vs Energy Density
  • 34. 9/14/2023 33 EIS Curves 2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0 -0.4 0.0 0.4 0.8 1.2 1.6 -Z"(W) Z'(W) Co3O4 @ 0% rGO (a) 1.7 1.8 1.9 2.0 2.1 0.0 0.2 0.4 0.6 0.8 Z'' (W) Z'(W) Co3O4 @ 5% rGO (c)
  • 35. 9/14/2023 34 EIS Curves 2.10 2.15 2.20 2.25 2.30 2.35 2.40 0.0 0.2 0.4 0.6 -Z"(W) Z' (W) Co3O4 @ 15% rGO (d) 1.4 1.5 1.6 1.7 -0.2 0.0 0.2 0.4 0.6 0.8 -Z"(W) Z'(W) Co3O4 @ 10% rGO (b)
  • 36. • Highly pure crystalline cubic structures are confirmed by XRD with average crystallite size of 24.4 Å • CV curves confirms the pseudo capacitive behavior of Co3O4 @ x % rGO composites • Comparatively, better energy and power densities are observed of Co3O4 @ 15% rGO composite along with longer discharging time • An unexpected specific capacitance at 2A/g is observed with Co3O4 @ 10% rGO 9/14/2023 35 Conclusion
  • 37. 9/14/2023 36 Co3O4 @ 15% rGO composite is preferable for practical device fabrication at low current densities Remarks
  • 38. 9/14/2023 37 Acknowledgment Center Of Excellence in Solid State Physics, PU Department of physics, COMSATS University US Pecas, NUST DS&T, University of Education Dr. Shahid Atiq Mr.Umer Waqas Mr. Amaar Tariq Special Thanks