Synthesis of Co doped MnO2 and study the

Supercapattery applications
Razzaq Ali
SAP : 21506
Supervised by : Dr. Amir Muhammad Afzal

2D Materials Research Lab

Department of Physics
Riphah International University,
Lahore, Pakistan.
 Outline

o Introduction
o Objective
o Methodology
o Result and discussion
o Conclusion
3
 Battery
• High energy density (≥ 150 Wh/kg)
. • High cycle life (≤ 2000 cycles)
• High columbic efficiency (≥ 95%)

SUPERCAPATTERY

Supercapacitor
. • Fast charge-discharge
• Excellent cyclability
• High power density (1-10 KW/Kg)
4
Properties of electrode materials
 Capacitor & Battery

Similarities Dissimilarities

6
 Objective

1 2 3
To synthesize the To investigate the To determine the
binary metal structural optimized
oxide analysis and CoMnO2
nanomaterial electrochemical electrode for
through properties of supercapattery
hydrothermal developed applications.
technique. materials.

7
 Methodology

Drying at 60Cͦ
MnO2 CoO2

Colloidal solution
of synthesized
nanomaterials
Precursor Solution
Washing several
times with
ethanol and DI
Hydrothermal Method water After grinding
 Electrochemical Measurements
Fabrication of Electrodes and Testing systems

1 2 3 4

Fabrication of Electrode 2-Electrode Assembly

Washing of Ni foam 9
3-Electrode Assembly
 Results and Discussion
We employed X-ray diffraction to characterize the structure. The XRD pattern of MnO 2

and CoMnO2. Using scherrer's formula, the crystalline size of MnO2 and CoMnO2 is
17.36nm and 17.46nm.
𝐷 = 𝐾𝜆/𝛽 cosθ

Where the D denotes the crystalline size, 𝜆 is the wavelength, 𝛽 is the full width and half
maximum. JCPDS No: 44-0141
1200 MnO2
1100 Co doped MnO2
1000
900
800
Intensity (a.u)

700

(211)
600
500
(110)

400 (200)

(400)
300

(411)

(521)
(600)
(301)
(220)

(002)

(312)
(541)
200

(601)
100
0
-100
10 20 30 40 50 60 70
2θ (degree)
10

XRD pattern of MnO2 and CoMnO2

 Results and Discussion

MnO2 Co doped MnO2

Average crystalline size is 70-150

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 Results and Discussion
Cyclic Voltammetry

150
0.20
3mV/s 3mV/s CoMnO2
5mV/s MnO2 0.15 10mV/s
100 10mV/s 20mV/s
20mV/s 0.10 30mV/s
(a) (b)
Current (mA)

50 30mV/s 40mV/s
40mV/s 0.05
50mV/s

B
50mV/s
0 0.00

-50 -0.05

-0.10
-100
0 10 20 30 40 50 60 70 0.0 0.1 0.2 0.3 0.4 0.5 0.6
Potential (V) vs Hg/HgO A

(a) and (b) cyclic voltammetry of manganese oxide and cobalt manganese oxide
50/50% at different scan rate (mVs-1).
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 Results and Discussion
Cyclic Voltammetry
0.12
MnO2 1200
0.10 MnO2
CoMnO2
0.08

Specific Capacity Cg-1

1000 CoMnO2
0.06
Current (mA)

0.04 (a) 800

(b)
0.02
600
0.00
-0.02 400
-0.04
200
-0.06
-0.08 0
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.00 0.01 0.02 0.03 0.04 0.05
Potential (V) Scane rate mV/s

Specific capacity comparison calculated from cyclic curves

Comparison of cyclic voltagram at 3mV/s.
in relation to scan rates (mV/s).
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 Results and Discussion
Galvanostatic Charge-discharge

(a) (b)

0.6 0.6 CoMnO2

MnO2
0.5 0.5

Potential (V)
Potential (V)

0.4 0.4
1.1A/g 1.0A/g
1.5A/g 1.5A/g
0.3 0.3
1.0A/g 2.0A/g
2.5A/g 2.5A/g
0.2 0.2
2.0A/g 3.0A/g
3.5A/g 1.2A/g
0.1 0.1
4.0A/g 1.5A/g
4.5A/g
0.0 0.0
0 300 600 900 1200 1500 1800 0 200 400 600 800 1000 1200 1400 1600
Time (Sec) Time (Sec)

GCD Curve of manganese oxide and cobalt manganese oxide electrodes at different
current densities.

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 Results and Discussion
Galvanostatic Charge-discharge

(a) (b)
800
0.6
700 CoMnO2

Specific Capecity (A/g)

0.5 MnO2
600
Ptential (V)

0.4
MnO2 500
0.3 CoMnO2 400
0.2 300

0.1 200

0.0 100
0 200 400 600 800 1000 1200 1400 1600 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Time (s) Current Density A/g

Galvanostatic charge-discharge comparison of Specific capacity calculated from the GCD curve is
electrodes at 1.0A/g. compared at different current densities. 15
 Results and Discussion
Specific Capacities

0.12
MnO2
At 3mV/s At 1.0 A/g 800
0.10
CoMnO2 Sample Specific Sample Specific 700 CoMnO2
0.08
Name capacity Name capacity

Specific Capecity (A/g)

MnO2
0.06 600
Current (mA)

0.04 (a)
0.02
MnO2 584.31 MnO2 360.9
500

400
0.00
-0.02 CoMnO2 1141.42 CoMnO2 713.25
300
-0.04
200
-0.06
-0.08 100
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Current Density A/g
Potential (V)

• “m” is the mass of active • “m” is the mass of active

materials (g) materials (g)
• “v” is the scan rate (mV/s) • “t” is discharging time (s)
• “I” is the current (mA) • “I” is the current (mA)
• “V” is the potential (V)
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(1)-Lee, C. C., et al (2017). Journal of Solid State Electrochemistry, 21(11), 3205-3213.
(2)-Omar, F. S., et al (2018. Electrochimica Acta, 273, 216-228.
 Results and Discussion
Supercapattery Assembly

0.04 1.8
3mV/s
R_CoMnO2 5mV/s 1.6 R_CoMnO2
10mV/s 1.4
0.02 20mV/s
1.2
Current (mA)

Potential (V)
30mV/s
1.0A/g
40mV/s 1.0
1.5A/g
50mV/s 0.8 2.0A/g
0.00 60mV/s
0.6 2.5A/g
70mV/s
3.0A/g
80mV/s 0.4
3.5A/g
90mV/s 0.2
-0.02 4.0A/g
100mV/s
0.0
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 0 50 100 150 200
Potential (V) Time (sec)

CV of the real device at various scan rates. GCD curve at various current densities.

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 Results and Discussion
Supercapattery Assembly
120 104
108C/g
100

Power Density (Wh/Kg)

Specific Capacity (C/g)

103
80
Energy Density = 24W/Kg
102
60 Power Density = 3200Wh/Kg

40 101

20
100
1.0 1.5 2.0 2.5 3.0 3.5 4.0 8 10 12 14 16 18 20 22 24 26
Current Ddensity (A/g) Energy Density (W/Kg)

Specific capacity of CoMnO2 device calculated from Plot exploring the energy density as a function of power density.
GCD curve.

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 Results and Discussion
Supercapattery Assembly

120 110 140 120

110 Chrrging Time 100 Efficiency (%) 110
100 Discharging Time 90 120 Charge C(F/g) 100
90

Discharging Time (s)

90 80
Chrrging Time (s)

100 80

Charge C(F/g)
80 70

Efficiency (%)
70 60 70
80 60
60 50
50
50 40 60
40
40 30 30
30 20 40
20
20 10 20 10
10 0 0
0 -10 -10
0 200 400 600 800 1000 0 200 400 600 800 1000
No.Of Cycle No.of Cycle

Charge discharge time measured of the device Stability measurement of the device observed
observed for 1000 cycle.
for 1000 cyclic charge discharge.

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 Conclusion
 In conclusion, cobalt Manganese Oxid, and Manganese Oxid were
synthesized through the hydrothermal method.
The electrochemical investigations showed the excellent performance of
synthesized nanomaterials in three electrode setup.
MnO2 specific capacity by GCD is 360.9 C/g and CoMnO2 specific
capacity is 713.25 C/g.
Asymmetric supercapacitor device (CoMnO2) showed specific capacity
108 C/g and energy density of 24 W/kg at power density of 3200 Wh/kg.

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 Acknowledgement

All praise goes to Almighty Allah the most Merciful and the most Beneficent, who
strengthened me with the capability to accomplish this research.

I would like to acknowledge my supervisor Dr. Amir Muhammad Afzal and Lab
Engineer Tasawer Abbas for his continuous support, guidance and encouragement
throughout my research work.

My sincere thanks also goes to the Department of Physics and I would like to thanks
all my 2D Materials Research Laboratory members and all the friends for their
cooperation, support and providing enjoyable moments.

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Thanks!