Ph.

D thesis defense

DEVELOPMENT OF CuO+Co3O4 NANOCOMPOSITE

NANOWIRES BY ELECTROSPINNING AS A
SUPERCAPACITOR ELECTRODE WITH HIGH ENERGY
DENSITY, POWER DENSITY AND RATE CAPABILITY

Baiju Vidyadharan
PSM12001

Main Supervisor : Prof. Jose Rajan

Co-supervisor : Prof. Mashitah Mohd. Yusoff
Energy and life
Energy storage devices are important to maintain
high quality modern life wherever transmission
lines are not available
Energy storage domain

How much energy the device can How fast it can be charged or discharged?-
store?- energy density (ES ) power density (PS)

107
Capacitors

106
Power density (W kg-1)

105
The Future

104
103 Supercapacitors Power density is
Supercapacitors
(SCs) compromised for
102 (SCs)
Batteries energy density!
10

1
10-2 10-1 1 10 102 103
Energy density (Wh kg-1)
Why ?
High energy
High power density
density
Supercapacitor
Supercapacitor
One electrode
Electrodes is made
made up up
of of ceramic
carbon
material
materials

Charge transfer occurs across

Accumulation of charge at the
the ceramic electrode-electrolyte
electrode-electrolyte
interface (Faradic process/
interface(EDLC)
pseudocapacitance)

No charge
Low transfer
power across
density the of
because interface
Rapid Charging
resistance and discharging
involved in the
charge transfer
Asymmetric Supercapacitor
Symmetric Supercapacitor
Problem statement

Energy and power density show an inverse

relationship in supercapacitors. Uniting them in a
single device is an elusive issue.
Requirements for high Es & Ps

• High electrochemical reversibility for long cycle life

• Multiple oxidation states to achieve high capacitance

• A high surface area to enable large electrode – electrolyte

interface

• High electrical conductivity for fast charge-discharge

Oxidation states and conductivity

102
4000
Conductivity (S cm-1)

10
3500
1
3000
2500
10-1
Cs(F g-1)

2000
10-2
1500
10-3

1000
10-4
  =1

  =4
=1
  =1

  =4
10-5
  =4
500
 

CuO NiO RuO2 MnO2 Co3O4 V2O5

Theoretical Cs Cs achieved Conductivity
∆  𝜹 − 𝐍𝐨 . 𝐨𝐟 𝐫𝐞𝐝𝐨𝐱 𝐜𝐨𝐮𝐩𝐥𝐞𝐬
Hypothesis

A composite of electrochemical materials having multiple

oxidation states and high electrical conductivity is likely to
generate a material with high Es and Ps

The composite should be in the form of One-dimensional

(1D) ultrafine nanowires due to their guided charge
transport properties.
Objectives

To develop ceramic nanowires of CuO, NiO, Co3O4,

NiO+CuO composite and Co3O4+CuO composite.

To study the electrochemical properties and energy

storage capabilities of the ceramic nanowire electrodes.

To fabricate ASCs and to evaluate their energy storage

capabilities.
 Methodology
Objective 1 Highly
crystalline
Synthesis of ceramic nanowires
Characterization of
nanowires using Diameter
electrospinning method ceramic nanowires
< 150 nm

Objective 2

Prepare slurry using ceramic

Evaluate the electrochemical
nanowire, conducting carbon and
properties of as prepared
PVDF in the ratio 75:10:15 and coat
ceramic nanowire electrode
on a Ni foam current collector

Develop an asymmetric
Optimize the device and
supercapacitor device and
calculate its energy and
evaluate its electrochemical
power density
properties
Objective 3
Achieving Objective 1
Synthesis of ceramic nanowires by Electrospinning
 Morphology of the ceramic nanowires

Figure (a) FESEM image of as prepared PVA/metal acetate composite wire

(b) Ceramic nanowire after calcination at 500 °C
(c&d) Bright field TEM images of ceramic nanowire
 Summary of diameter and particle size of nanowire observed from
FESEM and TEM images

Ceramic oxide Diameter   Particle size

from TEM
As-prepared Annealed

CuO 250 nm ~30- 50 nm 10 -20 nm

NiO - ~50-70 nm 10 -20 nm

Co3O4 - ~30 -60 nm 2-10 nm

NiO+CuO composite - ~ 90- 120 nm -----

Co3O4+CuO composite - ~ 120- 165 nm 15-20 nm

 Crystal structure of ceramic nanowires
obtained from XRD, SAED and HRTEM

2000
5000
Monoclinic
Face
(002)
(111)
(200)

4000
Co acentered
= 4.598 Å,
3O4
NiO
1500
(a.u)

CuO =Cubic
Intensity(a.u)

3000 bcubic
3.46 Å,
(111)

c= a = 8.051
Å &Å
1000
a =5.135
Intensity

4.18 Å
(220)
(202)

2000
β = 99.30o
(022)

(113)
(311)
(110)

(113)
(020)

(004)
(311)

500
(222)

1000

0
0
10 20 30 40 50 60 70 80
10 20 30 40 50 60 70 80
2(degree)
2(degree)
Crystal structure of composite nanowires
Conclusions of First objective

Composite of two different materials are achieved in a

single nanowire using electrospinning
 Achieving Objective 2

Electrochemical properties and energy storage

capabilities of the ceramic nanowire electrodes

b
b. 3 electrode configuration
a. Ceramic nanowire electrode WE – Working electrode
CE - Counter electrode
RE - Reference electrode
Cyclic voltammograms

1200 CuO
NiO
1000 Co3O4
NiO+CuO composite
800

Cs (Fg -1)
CuO+Co3O4 composite

600

400

200

0 10 20 30 40 50 60 70 80
-1
Scan rate (mVs )
Coulombic efficiency
Composite wire electrode ~ 99%
Single component electrode ~ 98%
Galvanostatic discharge curves

Dependence of Cs with
current density
CuO
NiO
1200
Co3O4
NiO/CuO composite
Co3O4/CuO composite
900

CS(Fg-1)
600

300

0 3 6 9 12 15 18 21
Current density (Ag-1)
 Conclusions of Second objective

Nanocomposite electrodes have Superior capacitance

and rate capability
Achieving objective 3

Fabrication and testing of asymmetric

supercapacitors using ceramic nanowires and
commercial activated carbon
Cyclic voltammograms

Dependence of Cs with scan rate

a b
240

210 AC//AC
CuO//AC
180 Co3O4//AC

Cs (Fg-1)
Co3O4/CuO//AC
150

120

c d 90

60

30
0 10 20 30 40 50 60
Scan rate (mVs-1)

a. Symmetric Supercapacitor (Control device)

b, c & d. Asymmetric Supercapacitors
Galvanostatic discharge profile
Dependence of CS with current
density
AC//AC CuO//AC
180
AC//AC

150 CuO//AC
Co3O4//AC
120 Co3O4/CuO//AC

Cs (Fg-1)
90
Co3O4//AC Co3O4+CuO//AC
60

30

0 2 4 6 8 10 12 14 16
Current density (Ag-1)
Uniting energy and power densities in
supercapacitors
60
Energy density (Whkg-1)

50

40 AC//AC
CuO//AC
30 Co3O4//AC
Co3O4+CuO//AC
20

10

0 3 6 9 12 15
Power density (kWkg-1)
Conclusions
1. CuO and Co3O4 nanostructures were generated in same
nanowire thereby formed a nanocomposite nanowire.

2. The nanocomposite nanowire showed superior

electrochemical properties than their individual
components.

3. Asymmetric supercapacitors using the nanocomposite

nanowire and activated carbon showed increased power
density without compromising the energy density.
Publications:
 
B.Vidyadharan, I. I. Misnon, R.A .Aziz, J. Ismail, M.M.Yusoff, and R. Jose, “High energy and
power density asymmetric supercapacitor based on electrospun cobalt oxide nanowire
anode” J. of Power Sources270(2014)526-535
 
B.Vidyadharan, M.K. Mohd. Zian, I. I. Misnon, R.A. Aziz, J. Ismail, M.M. Yusoff, and R. Jose,
“High performance supercapacitor electrodes from electrospun nickel oxide nanowires”,
J. of Alloys and Compounds 610(2014) 143-150

B.Vidyadharan, I. I. Misnon, R.A. Aziz, K. P. Padmasree, M.M.Yusoff, and R. Jose, “Superior

Supercapacitive performance in electrospun Copper oxide nanowire
electrode”J.Mater.Chem.A,2014,2,6578
 
I. I. Misnon, R. A. Aziz, M.K. Mohd.Zian, B. Vidyadharan, S.G. Krishnan, and R. Jose, “High
performance MnO2 nanoflower electrode and the relationship between solvated ion size
and specific capacitance in highly conductive electrolyte.” Material Research Bulletin
57(2014)221-230
 
Patents:
R. Jose, B.Vidyadharan, I. I. Misnon, R. A. Aziz, and M.M.Yusoff, "Highly
efficient energy storage devices developed from electrospun CuO, NiO and
Co3O4 nanowires" PI No.2013003071
 R. Jose, B.Vidyadharan, I. I. Misnon, R. A. Aziz, J. Ismail, and M.M.Yusoff,
"High Energy Density Supercapacitors from Transition Metal Doped Titanium
Dioxide Nanostructures" PI No. 204701623
Conference Proceedings:
B.Vidyadharan, I. I. Misnon, M.M. Yusoff, and R. Jose; “Electrochemical properties of
electrospun CuO nanowires” National Conference on Postgraduate Research 2012
(NCON-PGR 2012), Universiti Malaysia Pahang, September 2012
B.Vidyadharan,I. I. Misnon, and M.M. Yusoff, R. Jose “Highly efficient supercapacitors
developed from electrospun NiO nanowires” The 5th International Conference on
Postgraduate education (ICPE-5 2012),Universiti Teknology Malaysia, Johor 6-7
December 2012 (Malaysia)
B.Vidyadharan,I. I. Misnon, and M.M. Yusoff, R. Jose “Highly efficient supercapacitors
developed from electrospun Co3O4nanowires” The 5th regional conference on
Material Engineering and The 5th Regional Conference on Natural Resources&
materials
B.Vidyadharan,I. I. Misnon, and M.M. Yusoff, R. Jose “Highly efficient supercapacitors
developed from electrospun Ni- doped TiO2 nanowires” The Joint International
Conference on Nanoscience, Engineering and Management (BOND21) Penang
Awards and Medals:
“Highly efficient Supercapacitors developed from electrospun CuO nanowires,”
Bronze Medal, MTE 2013
“High energy density cum power density Supercapacitors from engineered materials”,
Gold medal, CITREX 2013
“High energy density cum power density Supercapacitors from engineered materials”,
Silver medal, ITEX 2013
“A High energy density transition metal oxide nanowire supercapacitor”, Gold medal,
CITREX 2014
“A High energy density transition metal oxide nanowire supercapacitor”, Silver
medal, ITEX 2014
“POWER ON ”, Diamond ,Platinum and gold medals, BIS London 2014
Thank You
Electrospinning Method

The build up of electrostatic charge on the surface

of a liquid induces the formation of jet, which is
then stretched to form a continuous fibre.The
solvent evaporates before it reaches the collector

Controlling parameters

I. Solution
A. Conductivity
B. Viscosity
C. Surface tension
D. Molecular weight
II . Process

A. Needle to collector
distance
B. Strength of electric field
C. Flow rate
III. Ambient
A. Humidity
 Comparison between previous and present protocol

  Reported method Present method

 

Polymer used Polyvinyl alcohol (PVA) Mw Polyvinyl alcohol

80000 Mw 95000 - 145000

PVA solution in water 10 wt% 7 wt %

 

  20 g PVA solution added into a Add a given amount of metal acetate

Procedure followed to prepare viscous solution containing 1 g Copper precursor into PVA solution to prepare
solution for electrospinning acetate and 2 g water a 0.24 m stock solution. Can be used
to prepare any ceramic oxide
nanowire from metal acetate precursor
 

  The solution is heated at 50 °C for 5 Stirred for 5- 8 hours for homogeneity

hours  

  As prepared wires was dried at 70 °C Calcined at 500 °C at a rate of 120

Procedure to get final ceramic for 5 hours °C/h for 1 hour
nanowire Calcined at 700 ° C at a rate of 240
°C per hour for 10 hours

Ceramic oxide wire properties Diameter ~ 200 – 450 nm Diameter 30 – 60 nm

Mw = 249 x 0.24

= 59.79
= 1.79 g
A summary of the optimized electrospinning method used in this
work. Amount of PVA used was 15 g; the solution stirred for 8
hours; electrospinning was carried out 25 kV at a solution feed rate
of 1 mL/hr.

Ceramic oxide Metal precursor used Amount (g) Solution

viscosity(cP)

PVA solution      

CuO Copper acetate monohydrate 0.7 77.3

NiO Nickel acetate tetrahydrate 0.8 77.8

Co3O4 Cobalt acetate tetrahydrate 0.82 77.6

NiO+CuO Copper acetate 0.4 78.1

composite Nickel acetate tetrahydrate 0.45

Co3O4+CuO Copper acetate 0.4 78.4

composite Cobalt acetate tetrahydrate 0.46
 Lattice parameters of materials obtained
from XRD

Material Space group Lattice parameters

a (Å) b Å) c (Å) α° ° °
CuO C12/c1, #15 4.598 3.46 5.135 90 99.3 90
NiO Fm3m 4.18 -- -- 90 90 90
Co3O4 Fd 3m : 2 8.051 --- --- 90 90 90
NiO/CuO The two phases were chemically distinguishable and their
crystal structures remained same
Co3O4/CuO The two phases were chemically distinguishable and their
crystal structures remained same
The specific surface area, total pore volume
and mean pore size of all materials

Materials Surface area (m2g-1) Pore volume Mean pore size

(cm3g-1) (nm)
CuO 14.5 0.5 11.5
NiO 13.7 0.5 10.6
Co3O4 13.5 0.4 11.2
CuO+Co3O4 14.7 0.5 11.3
NiO+CuO 14.1 0.5 11.6
Morphology of CuO
Morphology of NiO
Morphology of Co3O4
Cyclic Voltammograms Profile

E
% material utilization 1 2

35
CS  
mv( E2  E1 ) E1
i ( E )dE

30 CuO
Co3O4
25 NiO
n (%)

20

15

10 C S mV
n
5
0 10 20 30 40 50 FZ
Scan rate ( mVs-1)
 
  
Ch arg ing
_
2CuO  H 2O  2e Cu2O  2OH
 
Disch arg ing


Ch
arg

ing
 _
Cu(OH ) 2  e CuOH  OH
 
Disch arg ing

NiO + OH- ↔ NiOOH + NiO + e-

Ch
arging 
/ reduction
_
Co3O4  4 H 2O  2e  3Co(OH ) 2  2OH
    
Disch arg ing / oxidation

Ch
arg

ing
 _
3CoOOH  e  Co3O4  OH  H 2O
  
Disch arg ing
Galvanostatic charge/discharge Curve

It
CS 
mV

a. AC//AC b. CuO//AC c. Co3O4//AC d. Co3O4+CuO//AC

Electrochemical impedance spectroscopy of
samples (EIS)

Sample Rs (Ω) Rct (Ω) Peak Relaxation

frequency (fo) time (s)
(Hz)
CuO 0.56 0.32 3.9 0.25
NiO 0.76 1.3 1.02 0.9
Co3O4 0.82 1.4 0.40 2.5
NiO+CuO 0.43 0.82 0.25 3.9
Co3O4+CuO 0.48 0.71 12.07 0.083
 50 300
0.18

0.15
40 0.12
250

Z'' (
0.09

30
0.06
200
0.03
Z'' (

0.30 0.33 0.36 0.39 0.42

Z' (
150
20

100 R CT CP E PC ZW
10 RS
1 .4 8 W 3 7 m Fs 1 / 0 .7 9
50 C P E E D LC
0 .7 9 W
0
0 10 20 30 40 50
0 4 .8 m Fs 1 /0 .6 6
Z' ( 0 50 100 150 200 250 300
Summary of internal resistance and CS calculated from
discharge curves

Sample VIR ID Internal CS

( mV) (mA) resistance (Ω) (Fg-1)
CuO 8 5 1.6 657
NiO 3 2.2 1.4 694
Co3O4 8 4.6 1.7 1105
NiO/CuO 6 5 1.2 712
Co3O4/CuO 2 2.5 0.8 1277
 C ( )  C ' ( )  C" ( )

C ' ( )   Z " ( ) 2
 Z ( )

C" ( )  Z ' ( ) 2
 Z ( )
ELECTROCHEMICAL CHARACTERIZATION OF COMMERCIAL ACTIVATED CARBON

a. CV at various scan rate

b. Dependence of Cs with scan rate
c. Charge –discharge curves
d. Discharge curves at various current density
e. Dependence of Cs with current density
f. Nyquist plot
 q  CS  V  m

m C S  ( PC )  V

m C S  ( EDLC)  V

= 620 x 0.4/187
= 1.32
 Cyclic stability at varying
Cyclic stability at 5 Ag-1
current density
 0.010
0.40

Potential (V)/ vs.Ag/AgCl

0.008 0.35
0.30
Current (A)

0.006 0.25
0.20
0.004
0.15
0.002 0.10
0.05
0.000 0.00
-0.05
-0.002 0 1 2 3 4 5 6
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Time (s)
Applied potential (V)
 ASC RS (Ω) Rct (Ω)

AC//AC 0.82 0.41

CuO//AC 0.61 0.19

Co3O4//AC 0.81 1.4

Co3O4/CuO//AC 0.71 0.6

1 2 5 10
CuO// 29.5 23.5 19.2 16.4 370
AC
800 1500 4000 8400
co3O4/ 47.6 35.6 20 8 200
/AC
1.3 3.5 7 7.4
Compo 53 51 45 44 350
site//A
C
1.6 4 9.5 14