Under Graduate Dissertation Work

DEVELOPMENT OF NON-AQUEOUS
ASYMMETRIC HYBRID SUPERCAPACITORS

BASED ON Li-ION INTERCALATED
COMPOUNDS
A PROJECT REPORT
Submitted by
A. NAKKIRAN
in partial fulfillment for the award of the degree

of
BACHELOR OF TECHNOLOGY
in
CHEMICAL AND ELECTROCHEMICAL ENGINEERING
CENTRAL ELECTROCHEMICAL RESEARCH INSTITUTE

KARAIKUDI – 630 006
ANNA UNIVERSITY :: CHENNAI 600 025

MAY 2007
1
ANNA UNIVERSITY :: CHENNAI 600 025
BONAFIDE CERTIFICATE
Certified that this project report titled “DEVELOPMENT OF NON-

AQUEOUS ASYMMETRIC HYBRID SUPERCAPACITORS
BASED ON Li-ION INTERCALATED COMPOUNDS”, is the
bonafide work of “A. NAKKIRAN”, who carried out the project
work under my supervision.
V.Nandakumar Dr.D.Kalpana
PROJECT CO-ORDINATOR PROJECT
SUPERVISOR
Dean (Academics) Scientist
Centre For Education EEC Division
CECRI CECRI
Karaikudi Karaikudi
2
ABSTRACT
Modern power sources concentrate on electric vehicle’s
applications. Supercapacitors are also finding wider applications in
that field too. In our present study, four hybrid supercapacitor cells
were fabricated using LiCo1-xAlxO2 (x = 0, 0.2, 0.4 and 0.6) as
cathodes respectively and carbon nano foam as anode. The electrolyte
here used was 1M LiClO4 in 50-50 volume mixture of Ethylene
carbonate and Propylene carbonate. Polypropylene is used as
separator. The cathode materials were synthesized using soft
combustion method from their respective nitrate precursors. Glycine
was used as fuel for the combustion reaction. The synthesized cathode
materials were characterized physically by Thermal analysis, XRD
and FTIR. The fabricated supercapacitors were characterized
electrochemically using cyclic voltammetry, impedance spectroscopy
and galvanostatic charge-discharge. The performance of the
supercapacitors was evaluated using the above characterizations. The
specific parameters of the supercapacitors were also calculated.
Among the four supercapacitors the one, which is having the
LiCo0.6Al0.4O2 composition as cathode, is having good capacitance
behaviour.
3
TABLE OF CONTENTS
CHAPTER TITLE
PAGE NO
NO.
ABSTRACT 3
LIST OF TABLES v
LIST OF FIGURES vi
LIST OF ABBREVIATIONS ix
LIST OF SYMBOLS x
1. INTRODUCTION 15
1.1 Different types of energy storage devices 16
1.1.1 Conventional Capacitors 16
1.1.2 Batteries 18
1.1.2.1 Primary Batteries 19
1.1.2.2 Secondary Batteries 19
1.1.2.3 Emergence of Lithium Batteries 19
1.1.2.4 Cathode Materials for Li Ion Batteries 22
1.1.3 Supercapacitors 23
1.1.3.1 Advantages of Supercapacitors 29
1.1.3.2 Limitations of Supercapacitors 30
1.1.3.3 Electrodes for Supercapacitors 30
1.1.3.4 Classification of Supercapacitor 32
REFERENCES 37
2. LITERATURE REVIEW 41
2.1 Review on Carbon Electrodes 41
4
2.2 Review on Electrolytes 44
2.3 Review on Lithium Compound Electrodes 47
2.4 Review on Hybrid Supercapacitors 49
REFERENCES 50
3. SCOPE AND OBJECTIVE 55

3.1 Advantages of Hybrid Supercapacitors 56
3.2 Advantages of LiCoO2 57
3.3 Advantages of CNF 58
3.4 Advantages of Non-Aqueous Electrolyte 59
REFERENCES 59
4. EXPERIMENTAL 61
4.1 Synthesis of Cathode Material 61
4.1.1 Existing Methodologies for the Synthesis of
Cathode materials 61
4.1.2 Need to Identify Suitable Synthesis Methods 44
4.1.3 Soft Combustion Method 62
4.1.4 Synthesis Procedure 65
4.1.5 Flow chart for synthesis 66
4.1.6 Annealing 67
4.2 Physical Characterization Techniques 67
4.2.1 Thermal Analysis 67
4.2.1.1 Thermo-Gravimetric Analysis 67
4.2.1.2 Differential Thermal Analysis 68
4.2.2 Fourier Transform Infra Red Spectroscopy 70
4.2.3 X-Ray Diffraction 72
5
4.3 Cell Fabrication 74
4.3.1 Composition for Positive Electrode 74
4.3.2 Composition for Negative Electrode 75
4.3.3 Steps Involved in Cell Fabrication 75
4.4 Electrochemical Characterization Techniques 77

4.4.1 Cyclic Voltammetry 77
4.4.2 Electrochemical Impedance Spectroscopy 79
4.4.3 Galvanostatic Charge-Discharge Cycle Tests84
REFERENCES 84
5. RESULTS AND DISCUSSION 87

5.1 Thermal Analysis 87
5.1.1 Thermo-Gravimetric Analysis 87
5.1.2 Differential Thermal Analysis 88
5.2 FTIR Spectroscopy 88
5.3 X-Ray Diffraction 91
5.4 Cyclic Voltammetry 93
5.5 Electrochemical Impedance Spectroscopy 100
5.6 Galvanostatic Charge-Discharge Cycle Tests 102
6. CONCLUSIONS 110
6
LIST OF TABLES
TABLE TITLE
PAGE NO.
NO.
1.1 Parametric comparison among capacitor, supercapacitor
4.1 Typical materials prepared by combustion method 64
4.2 Composition for synthesis of LiCo(1-x)AlxO2
(x = 0, 0.2, 0.4, 0.6) 66
5.1 Specific capacitance (F/g) values of LiCo(1-x)AlxO2
(x = 0, 0.2,0.4, 0.6) as calculated from cyclic
voltammograms 99
5.2 Solution resistance (Rs) and double layer capacitance
(Cdl) values of LiCo(1-x)AlxO2 (x = 0, 0.2, 0.4, 0.6)
as calculated from electrochemical
impedance spectrographs 102
5.3 Various parameters of supercapacitors fabricated using
the synthesized cathode materials as calculated
from galvanostatic charge-discharge tests 108
7
LIST OF FIGURES
FIGURE TITLE
PAGE NO.
NO.
1.1 Construction of a conventional capacitor 17

1.2 Schematic representation of conventional capacitor 17
1.3 The formation of double layer during the charging 23
1.4 Ragone’s plot for different energy storage systems 24
1.5 Charge/Discharge profile comparison 27
1.6 Classification of supercapacitors 33
1.7 Charging at electrode surface 34
1.8 Ragone’s plot 36
3.1 Layered structure of LiCoO2 58
4.1 Diagram of Thermo Gravimetric Analyzer 68
4.2 Construction of Differential Thermal Analyzer 69
4.3 Layout of FTIR spectrometer 71
4.4 Binder, Spatula, Mortar and Pestle 75
4.5 A dried single electrode 76
4.6 Electrodes tied using nylon thread 77
4.7 A fully fabricated supercapacitor cell 77
4.8 Schematic explanation of a cyclic voltammetry
experiment in the absence of a redox couple 79
4.9 Magnitude of the resultant sine wave as a function of
frequency for a representative standard test cell with one
layer of Celgard 2500 80
8
4.10 Phase difference between the incident and resultant wave
forms 80
4.11 The real portion of the resultant wave form as a function of
frequency 81
4.12 The imaginary portion of the resultant wave form as a
function of frequency 81
4.13 The resistance of the resultant waveform as a function 83
4.14 The capacitance of the resultant waveform as a function of
frequency 83
5.1 TGA curves of base LiCoO2 and aluminium doped LiCoO2 87
5.2 DTA curves of base LiCoO2 and aluminium doped LiCoO2 88
5.3 FTIR spectrum of LiCoO2 89
5.4 FTIR spectrum of LiCo0.8Al0.2O2 90
5.7 XRD spectra of cathode materials 92
5.8 XRD spectra of cathode materials (2θ range from 35 to 41◦) 92
5.9 CV of LiCoO2/CNF supercapacitor as fabricated 95
5.10 CV of LiCo0.8Al0.2O2/CNF supercapacitor as fabricated 96
5.13 CV of LiCoO2/CNF supercapacitor after 500
Charge/discharge cycles 97
5.14 CV of LiCo0.8Al0.2O2/CNF supercapacitor after 500
Charge/discharge cycles 98
charge/discharge cycles 98
9
charge/discharge cycles 99
5.17 Electrochemical impedance spectroscopes of supercapacitors
before cycles 101
5.18 Electrochemical impedance spectroscopes of supercapacitors
5.19 2nd charge/discharge cycle of LiCoO2/CNF supercapacitor 104
5.20 500th charge/discharge cycle of LiCoO2/CNF supercapacitor 104
5.21 2nd charge/discharge cycle of LiCo0.8Al0.2O2/CNF
supercapacitor 105
5.22 500th charge/discharge cycle of LiCo0.8Al0.2O2/CNF
supercapacitor 105
supercapacitor 106
supercapacitor 106
supercapacitor 107
supercapacitor 107
10
LIST OF ABBREVIATIONS
EDLC - Electrochemical Double Layer Capacitor

DLC - Double Layer Capacitor
DC - Direct Current
RF - Radio Frequency
ESR - Equivalent Series Resistance
EC - Electrolytic Capacitor
CNF - Carbon Nano Foam
EV - Electric Vehicles
IR - Internal Resistance
TGA - Thermo-Gravimetric Analysis
DTA - Differential Thermal Analysis
FTIR - Fourier Transform Infra-Red
XRD - X-Ray Diffraction
SEM - Scanning Electron Microscope
IR - Infra-Red
NMP - n-Methyl Pyrrolidine
EC - Ethylene Carbonate
PC - Propylene Carbonate
EIS - Electrochemical Impedance Spectroscopy
CV - Cyclic Voltammetry/Voltammogram
AC - Activated Carbon
11
LIST OF SYMBOLS
C - Capacitance
Q - Charge
V - Voltage or Volt
ε - Dielectric constant
εo - Permittivity of vacuum
A - Area of electrode or Absorbance or Ampere
D - Distance between electrodes
0
C - Degree Celsius
µ - micro (10^-6)
F - Farad
W - Watt
h - Hour
k - Kilo (10^3)
g - Gram
tc - Charging time
td - Discharge time
m - Milli (10^-3) or Meter
Tm - Melting point
Tb - Boiling point
Tf - freezing point
G - Gibbs energy
T - Transmittance
I - Intensity of radiation or Magnitude of current
λ - Wavelength
d - Inter-atomic spacing
12
θ - Angle
E - Voltage drop / magnitude of voltage
v - Scan rate
ω - Frequency
t - Time
Z - Impedance
ZI - Real part of impedance
ZII - Imaginary part of impedance
R - Resistance
j - Imaginary Coefficient
c - Centi (10^-2)
13
Chapter-1
INTRODUCTION
14
1. Introduction
Energy and its storage devices are one amongst the principal concerns
of present day research. It is so important because, research in energy storage
devices indirectly solves a lot of problems by providing an effective
alternative for non-renewable resources like petroleum, diesel, etc. and also
contributes towards pollution control by developing battery powered vehicles
which are ecofriendly. Modern power electronics began with the advent of the
first power semiconductor devices in the 1950’s. Since then many inventions
of devices, converter circuits, controls, and applications have enriched the
field. Since the early 1980’s power electronics has emerged as an important
discipline in engineering due to the introduction of new devices and
increasing popularity [1]. Power electronics systems or power processors
almost in every topology, with the exception of very special cases such as
matrix converters, have the need of energy storage devices to provide energy
backup and decoupling between different power conversion stages.
Traditionally due to their low cost the most commonly used storage devices
are capacitors and batteries, but they have some drawbacks such as size,
performance and life. There are several new energy storage technologies
available today that appear to be very promising options to the traditional
energy storage devices [2]. Among these new energy storage devices
supercapacitors appear to be a good option for applications that require high
power densities and fast transient response, and all this in a reduced volume.
Thus the energy storage devices may be divided into three types such as,
1) Conventional capacitors
2) Batteries and
3) Supercapacitors
15
1.1. Different types of energy storage devices
1.1.1 Conventional capacitors
Conventional capacitors consist of two electrodes separated by a thin

layer of dielectric material. Due to electronic and ionic polarisation of the
dielectric medium upon application of an electric field, electrical charge can
be stored at the electrodes [3]. The capacitance (C) can be calculated with
C = ∆Q/∆V……………………….………1.1
Where Q is the electrical charge stored at the electrodes and V the

applied potential difference between the electrodes. In an ideal capacitor the
capacitance does not change upon variation in the potential difference. The
capacitance can be increased by making use of a dielectric medium with a large
dielectric constant, increasing the electrode surface area or decreasing the
distance between the electrodes, since
C = (εεo A)/D…………………………….1.2
where ξr (also referred to as k) is the relative dielectric constant of the di-

electric medium, ξ the permittivity of vacuum, A the geometric
electrode surface area and D the distance between the electrodes. By
decreasing the distance between the electrodes, the electric field strength is
increased. If the electric field strength exceeds a certain threshold value called
the dielectric strength, the material will lose its insulating property.
16
Fig 1.1: Construction of a conventional capacitor
The above theory can be simply represented by the following schematic

diagram.
Fig 1.2: Schematic representation of conventional capacitor
17
1.1.2. Batteries
A battery is a device that converts chemical energy into electrical

energy by means of an electrochemical reduction-oxidation (redox) reaction.
With the ever-increasing market for portable electronic devices, e.g. cell-
phones, laptop computers, there is always an increased need for improved
energy sources. Most of the electronic products today use “state-of-the-art”
batteries, and yet the performance of these leaves much to be desired. Another
aspect is the environmental threat posed by the heavy metals used in many of
today’s battery concepts. As society is becoming more aware of these
problems, the desire for environmentally friendly battery components is
growing. Batteries may be classified into many types based on the cathode,
anode and the electrolyte used. The historical battery development has gone
from Copper/Zinc cell to Li-ion cell [4-6].
1. Copper/zinc (Volta, 1800)
2. Lead-acid (Planté, 1859)
3. Zinc/manganese-oxide (Leclanché, 1866) over zinc-air
(1878),
4. Ni-Cd (Jungner, 1899)
5. Sodium-sulphur (Yao & Kummer, 1966)
6. Li primary cells (1960’s) to the present technology of Ni-MH
(early 1980’s)
7. Li- ion secondary cells (early 1990’s).
Batteries may also be classified into two types based on their
electrode reactions. They are:
1.1.2.1. Primary batteries
1.1.2.2. Secondary batteries
18
1.1.2.1. Primary batteries
In primary batteries, the electrode reactions are not reversible and the
cells are therefore not rechargeable, i.e. after one discharge, they are
discarded.
For example: - Dry cell (Zn-MnO2), Ni-MH.
1.1.2.2. Secondary batteries
In secondary batteries, the electrode reactions are reversible and the

cells are rechargeable. For example:-Lead acid battery, Li-ion battery.
A battery comprises three main components: cathode, electrolyte and
anode. The cathode is characterized as the electrode where a reduction-
reaction occurs (i.e. electrons are accepted from an outer circuit), while an
oxidation-reaction occurs at the anode (i.e. electrons are donated to an outer
circuit) [7]. The electrolyte is an electronic insulator, but a good ionic
conductor; its main function is to provide a transport-medium for ions to
travel from one electrode to the other. It must also prevent short-circuiting by
acting as a physical barrier between the electrodes, either alone in the case of
a polymer or in the matrix it impregnates (the separator) if a liquid. The
voltage and capacity of a cell are functions of the electrode materials used.
1.1.2.3. Emergence of lithium batteries
One of the last century’s most revolutionary battery-related discoveries

was the interaction between alkali-metal-salts and polar polymers. These
compounds exhibit significant ionic conductivity and prompted Armand et al
19
[8] to make a more detailed electrical characterization, which led to the idea
of the all-solid-state lithium polymer battery concept. Originally, Li-metal
was used as anode in the secondary Li batteries, and an inorganic intercalation
or insertion compound as cathode. The first secondary Li/insertion-compound
system was the Li/TiS2 system, announced to be commercialized by Exxon in
the mid 1970’s. There are advantages with using metallic Li as anode in the
battery: the redox potential becomes very low and the equivalent weight is
also low. There are problems, however, associated with the use of metallic Li:
e.g. corrosion of Li by reaction with electrolyte,
Safety aspects where dendrite formation can cause short-circuiting of
the cell with a following thermal runaway and possible explosion. The
concept of Li ion transfer cells was proposed to solve these problems.
Nowadays, these are usually referred to as Li-ion cells. In these cells, an
insertion electrode, usually carbon-based, replaces the Li metal anode. In this
way, the active lithium is always present as an ion rather than as a metal.
Metallic lithium is highly reactive with oxygen, nitrogen and moisture,
making it a difficult material to handle; glove-boxes or dry-rooms becomes a
necessity in production.
Battery production can be simplified by using insertion electrodes as
both anode and cathode, since the battery components can be produced in
ambient atmosphere and then swelled with electrolyte in a controlled
atmosphere. Electrode materials other than insertion compounds have also
showed promising properties, e.g. polymeric cathodes and nano-particle
anodes [9-10]. To make a complete Li-ion cell, one of the electrodes will have
to contain Li-ions, which are then shuttled reversibly between the electrodes
during charge/discharge. A variety of electrodes have been tested over the
20
years but, for commercial purposes, the LiCoO2 electrode or variations
thereof have been the most exploited [11-13].
A big problem with the Li-ion concept is that any Li consumed by
secondary reactions cannot be retrieved, and the specific capacity is totally
dependent on the amount of Li available for the reversible redox process in
the cell. Some of the processes known to lead to capacity loss in Li-ion cells
are: Li deposition (in cell over-charge), electrolyte decomposition, active
material dissolution, phase changes in the insertion electrode materials, and
passive film formation on the electrode and current collector surfaces.
The distinguishing features of today’s commercial Li-ion batteries are
as follows.
High operating voltage: a single cell has an average operating potential
of approx. 3.6 V, three times the operating voltage of both Ni-Cd and
Ni-MH batteries and about twice that of sealed Pb-acid batteries.
Compact, lightweight, and high energy density: the energy density is
about 1.5 times and specific energy is about twice that of high-capacity
Ni-Cd batteries.
Fast charging potential; batteries can be charged to about 80-90% of
full capacity in one hour.
High discharge rate: up to 3C are attainable.
Wide range of operating temperature: from –20 to +600C.
Superior cycle life: service life of a battery exceeds 500 cycles.
Excellent safety: United States Department of Transportation,
Dangerous Materials Division has declared Li-ion batteries exempt
from dangerous materials regulations.
Low self-discharge: only 8-12% per month.
21
Long shelf-life: no reconditioning required up to approximately 5 years
(Ni-Cd: 3 months; Ni-MH: 1 month).
No memory-effect: can be recharged at any time.
Non-polluting: does not use toxic heavy
1.1.2.4. Cathode materials for Li-ion batteries
LiCoO2 is the most commonly used cathode material in commercial Li-

ion batteries today by virtue of its high working voltage, structural stability
and long cycle life. However, Co is an expensive metal and much effort has
been made in recent years to find a cheaper alternative.
LiNiO2 (isostructural with LiCoO2) and spinel type LiMn2O4 are
promising materials in this respect, where LiNiO2 is the more attractive
alternative because of its high specific capacity and better elevated-
temperature performance.
However, LiNiO2 has not been commercialized successfully for several
reasons: i) difficult synthesis conditions, ii) poor structural stability on cycling
and iii) poor thermal stability in the delithiated state as a result of the unstable
Ni4+ ion. One way to circumvent these problems is to partially substitute
nickel by other cations. Many recent studies focus on substituted compounds
of this general type [14-19].
Co substituted LiNiO2, LiNi1-xCoxO2 (V), has the advantage of
combining the favorable properties of LiNiO2 and LiCoO2. LiNi1-xCoxO2 is
known to have much higher structural stability than pure nickel oxide and
combined with its potentially lower cost than LiCoO2, is highly promising
material for practical application.
22
1.1.3. Supercapacitors
Supercapacitors are an advanced version of capacitors with unique

ability to combine energy storage capabilities of batteries and power storage
behavior of capacitor. Hence fill the gap between batteries and conventional
capacitors such as the electrolyte capacitors in terms of specific energy as
well as specific power.
Supercapacitor or Electrochemical Double Layer Capacitor (EDLC) is
complementary to secondary batteries for applications in hybrid power
systems like electric vehicles and memory backup systems etc [20]. The
supercapacitor resembles a regular capacitor with exception that it offers very
high capacitance in a small package.
Energy storage is by means of static charge rather than of an electro-
chemical process that is inherent to the battery. Applying a voltage
differential on the positive and negative plates charges the supercapacitor.
This concept is similar to an electrical charge that builds up when walking on
a carpet. The supercapacitor concept has been around for a number of years.
Newer designs allow higher capacities in a smaller size.Fig 1.4. Shows the
formation of double layer during charging.
Fig 1.3: Formation of double layer during the charging.
23
Fig 1.4: Ragone’s plot for different energy storage systems
Supercapacitor devices consist of two electrodes to allow a potential to

be applied across the cell, and there are therefore two double-layers present,
one at each electrode/electrolyte interface. An ion-permeable separator is
placed between the electrodes in order to prevent electrical contact, but still
allows ions from the electrolyte to pass through. The electrodes are made of
high effective surface-area materials such as porous carbon or carbon aerogels
in order to maximize the surface-area of the double-layer. High energy
densities are therefore achievable in EDLCs due to their high specific
capacitance, attained because of a high electrode/electrolyte interface surface-
area and a small charge layer separation of atomic dimensions. In addition to
24
the capacitance that arises from the separation of charge in the double-layer, a
contribution to capacitance can be made from reactions that can occur on the
surface of the electrode. The charge required to facilitate these reactions is
dependent on the potential, resulting in a Faradaic ‘pseudo capacitance’. Due
to the fundamental differences between double-layer capacitance and pseudo
capacitance, the two topics shall be discussed separately later.
The understanding of the electrical processes that occur at the boundary
between a solid conductor and an electrolyte was developed gradually.
Various models have been developed over the years to explain the phenomena
observed by chemical scientists. The widely accepted explanation that was
proposed by Bockris, Devanathan and Muller in 1963 [21]. They suggested
that a layer of water was present within the inner Helmholtz plane at the
surface of the electrode. The dipoles of these molecules would have a fixed
alignment because of the charge in the electrode. Some of the water
molecules would be displaced by specifically adsorbed ions. Other layers of
water would follow the first, but the dipoles in these layers would not be as
fixed as those in the first layer.
Pseudocapacitance arises from reversible faradaic reactions occurring
at the electrode, and is denoted as ‘pseudo’-capacitance in order to
differentiate it from electrostatic capacitance. The charge-transfer that takes
places in these reactions is voltage dependent, so a capacitive phenomenon
occurs. There are two types of reactions that can involve a charge transfer that
is voltage dependent. They are redox reactions and ion sorption reactions. In
summary, the high values of specific capacitance attainable through EDLC
technology are a result of double-layer capacitance, and often
pseudocapacitance. Double-layer capacitance offers good charge storage
capabilities thanks to possessing high surface-area materials as electrodes,
25
and the fact that charge separation occurs at atomic dimensions.
Pseudocapacitance that arises from redox or ion sorption reactions further
improves the achievable capacitance.
A regular capacitor consists of conductive foils and a dry separator; the
supercapacitor crosses into battery technology by using special electrodes and
some electrolyte. There are three types of electrode materials suitable for the
supercapacitor. They are: high surface area activated carbons, metal oxides
and conducting polymers. The high surface electrode material, also called
Double Layer Capacitor (DLC), is least costly to manufacture and is the most
common. It stores the energy in the double layer formed near the carbon
electrode surface. The electrolyte may be aqueous or organic. The aqueous
variety offers low internal resistance but limits the voltage to one volt. In
contrast, the organic electrolyte allows 2.5 volts of charge, but the internal
resistance is higher.
To operate at higher voltages, supercapacitors are connected in series.
On a string of more than three capacitors, voltage balancing is required to
prevent any cell from reaching over-voltage. The amount of energy a
capacitor can hold is measured in microfarads or µF. (1µF = 0.000,001 farad).
While small capacitors are rated in nano-farads (1000 times smaller than 1µF)
and pico-farads (1 million times smaller than 1µF), supercapacitors come in
farads.
The gravimetric energy density of the supercapacitor is 1 to 10Wh/kg.
This energy density is high in comparison to a regular capacitor but reflects
only one-tenth that of the nickel-metal-hydride battery. Whereas the electro-
chemical battery delivers a fairly steady voltage in the usable energy
spectrum, the voltage of the supercapacitor is linear and drops evenly from
full voltage to zero volts. Because of this, the supercapacitor is unable to
26
deliver the full charge. If, for example, a 6V battery is allowed to discharge to
4.5V before the equipment cuts off, the supercapacitor reaches the threshold
within the first quarter of the discharge cycle. The remaining energy slips into
an unusable voltage range. A DC-to-DC converter could correct this problem
but such a regulator would add costs and introduce a 10 to 15 percent
efficiency loss.
Fig 1.5: Charge/Discharge profile comparison
Rather than operate as a main battery, supercapacitors are more

commonly used as memory backup to bridge short power interruptions.
Another application is improving the current handling of a battery. The
supercapacitor is placed in parallel to the battery terminal and provides
current boost on high load demands. The supercapacitor will also find a ready
27
market for portable fuel cells to enhance peak-load performance. Because of
its ability to rapidly charge, large supercapacitors are used for regenerative
braking on vehicles. Up to 400 supercapacitors are connected in series to
obtain the required energy storage capacity. The charge time of a
supercapacitor is about 10 seconds. The ability to absorb energy is, to a large
extent, limited by the size of the charger. The charge characteristics are
similar to those of an electrochemical battery. The initial charge is very rapid;
the topping charge takes extra time. Provision must be made to limit the
current when charging an empty supercapacitor.
In terms of charging method, the supercapacitor resembles the lead-
acid battery. Full charge occurs when a set voltage limit is reached. Unlike the
electrochemical battery, the supercapacitor does not require a full-charge
detection circuit. Supercapacitors take as much energy as needed. When full,
they stop accepting charge. There is no danger of overcharge or 'memory'.
The supercapacitor can be recharged and discharged virtually an
unlimited number of times. Unlike the electrochemical battery, there is very
little wear and tear induced by cycling and age does not affect the
supercapacitor much. In normal use, a supercapacitor deteriorates to about 80
percent after 10 years.
The self-discharge of the supercapacitor is substantially higher than that
of the electro-chemical battery. Supercapacitors with an organic electrolyte
are affected the most. In 30 to 40 days, the capacity decreases from full
charge to 50 percent. In comparison, a nickel-based battery discharges about
10 percent during that time.
The comparison between supercapacitors, conventional capacitors and
batteries can be clearly explained by the table 1.1.
28
Table 1.1: Parametric comparison among capacitor, supercapacitor and
batteries.
Device Capacitors EDLC Battery
Charging time µ s–ms m s - minute hours

Discharge time µ s–ms m s – minute minutes– months
Cycle life 106 - 108 106 - 108 200-1000
Specific power > 10,000 1000-3000 <500

(W/kg)
Specific energy <0.01 0.5-5 50-300
(Wh/kg)
1.1.3.1. Advantages of supercapacitors
Low impedance - enhances load handling when put paralleled

with a battery.
Rapid charging -supercapacitors charge in seconds.
Simple charge methods - no full-charge detection is
needed; no danger of overcharge.
Extends battery run time.
Enables design to meet current specifications.
Cuts pulse current noise.
Lessens RF noise by eliminating DC/DC
Allows low/high temperature operation
Minimizes space requirements
29
Reduces battery size
Enhances load balancing when used in parallel with a battery
Meets environmental standards
Virtually unlimited cycle life - can be cycled millions of time.
1.1.3.2. Limitations of supercapacitors
Linear discharge voltage prevents use of the full energy

spectrum.
Low energy density - typically holds one-fifth to one-tenth the
energy of an electrochemical battery.
Cells have low voltages - serial connections are needed to obtain
higher voltages. Voltage balancing is required if more than three
capacitors are connected in series.
High self-discharge - the rate is considerably higher than that of
an electrochemical battery.
1.1.3.3. Electrodes for supercapacitors
The following are used as electrode materials for Supercapacitor.
Carbon
Metal oxides
Conducting Polymer
30
Carbon
Carbon-Carbon supercapacitors use the cheapest technology due to the

low price of activated carbon. These system functions on the basis of Gouy-
Chapmann and Stern-Geary electrochemical double layer theory [22]. On the
basis of the mechanism for double layer formation, it is generally true that the
layer surface area that an EDLC can provide for adsorption of electrolytes on
electrodes, the more energy can be stored in the EDLC. Activated carbons
with large surface area and porosity are suitable candidates as materials for
the polarizable electrodes in EDLC. There is no charge-transfer reaction
occurring during the charge-discharge process. Cyclability of these
supercapacitors is very high. Both non-aqueous and aqueous electrolyte can
be used. Organic electrolyte leads to a larger electrochemical window than the
aqueous one. It is then possible to increase the voltage up to 3V but the
Equivalent series resistance is usually high that precludes to reach easily high
powers. Supercapacitor voltage is limited to 1V the thermodynamic window
of water is 1.23V with a relatively low Equivalent Series Resistance (ESR)
with aqueous electrolyte based supercapacitors.
Metal oxides
In metal oxide, pseudocapacitance is developed due to the redox

reaction. As a result, metal oxide supercapacitors generally have a very high
capacitance. Conducting metal oxides like RuO2 or IrO2 were the favorable
electrode a material in early EC’s used for space for military applications. The
31
high capacitance in combination with low resistance resulted in very high
powers [23].
Conducting polymer
Conducting polymers are low cost materials and they have been found
as electrode materials for supercapacitor applications. Polymeric materials,
such as p and n doped poly (3-arylthiopene), p-doped poly (pyrrole), poly 93-
methylthiophene) or poly (1, 5 – daaminoan thraquinone) have been
suggested by many authors. The cyclic voltammogram of a polymer exhibits
a current peak at the respective redox potential of the polymer. These types
of electrodes are used in both aqueous and non-aqueous media and are
reported to yield high energy density and power density [24]. The drawbacks
linked with these conducting polymer, are slow electrochemical kinetics and
swelling or shrinking of electrode materials in solution during the charge-
discharge process.
1.1.3.4. Classification of supercapacitors
Based on the electrode materials listed above the supercapacitors may

be classified as:
Electrochemical double layer capacitors

Pseudocapacitors or ultra capacitors
Hybrid capacitors
32
The detailed classification is explained in Fig 1.6.
Fig 1.6: Classification of supercapacitors
Electrochemical double layer capacitors
The term electrochemical double layer capacitor is most commonly

used for carbon based double layer capacitors because of its high
capacitance value. It generally denotes the supercapacitor having non-
faradaic reactions at both electrodes
33
Error!
Fig 1.7: Charging at electrode surface
Advantages
High surface area and double layer of charge allows for much
higher densities than conventional capacitors, comparable
power densities.
No chemical or structural change during charge storage—106
cycles for supercapacitors compared to 103 for batteries
Work in extreme temperatures and are very safe
34
Nanostructured carbon are relatively cheap and have well
developed fabrication techniques
can achieve wide range of pore distribution, thus energies and
powers
Disadvantages
cannot match energy densities of mid level batteries
Pseudocapacitors or ultra capacitors
In a pseudocapacitor, there are two basic reactions, which lead to

electrochemical cell. Both occur at the interface between a conductor and an
electrolyte and both benefits form very high specific surface areas at the
electrode. The first mechanism commonly referred to as charge separation,
which is well documented as non-faradaic mechanism and is the basis for
EDLC. The second reaction commonly referred to as an oxidation –
reduction reaction due faradaic mechanism.
Advantages
High surface area and fast faradic reactions allow for higher
energy densities than EDLCs
Hydrous ruthenium oxide can achieve extraordinary
capacitances
Disadvantages
35
Generally lower energy densities than EDLCs
Cycle life can be limited by mechanical stress caused during
reduction oxidation reactions
Negatively charged conducting polymer electrodes are not very
efficient
The best metal oxide electrodes are very expensive and require
an aqueous electrolyte which means lower voltage.
Hybrid supercapacitors
Hybrid power system is a new highly reliable energy storage device. It

is a combination of EDLC and a battery. (e.g. C and Li-ion).
Fig 1.8: Ragone’s plot
36
Advantages
Most flexible performance characteristics of supercapacitor—fit

the widest range of applications.
can achieve very high energy and power densities without
sacrifices in cycling stability and affordability
Disadvantages
Relatively new and unproven technologies

More research is needed to understand the full potential of
hybrid capacitors.
References
1. N. Mohan, T.M. Underland and W.P. Robbins, Power Electronics,

Converters, Applications and Design, New York: John Wiley &
Sons, 1995.
2. M. Stanley Whittingham et al, Chemical Reviews, 104, 10, (2004)

P.4243-4244.
3. R. Kötz and M Carlen, Electrochimica Acta, 45 (2000) P.2483.
4. Handbook of Batteries, 2nd edition, D. Linden, Ed., McGraw-Hill,

Inc., New York (1995).
37
5. T. Nagaura and K. Tozawa, Progress in Batteries and Solar Cells, 9
(1990) P.209.
6. P.G. Bruce, Solid State Electrochemistry, P.G. Bruce, Ed.,

Cambridge University Press, Cambridge, 1995.
7. M.S. Whittingham, Science, 192 (1976) P.1126.
8. M.B. Armand, Materials for Advanced Batteries, D.W. Murphy, J.

Broadhead, B.C.H. Steel, Eds., Plenum, New York, 1980, P.145.
9. A.S. Gozdz, C.N. Schmutz, and J.M. Tarascon, U.S. Pat. 5,296,318
(1996).
10. N Oyama, T. Tatsuma, T. Sato, and T. Sotomura, Nature, 373 (1995)

P.598.
11. D.W. Murphy and P.A. Christian, Science, 205 (1979) P.651.
12. M. Winter, J.O. Besenhard, M.E. Spahr, and P. Novák, Advanced

Materials, 10 (1998) P.725.
13. R. Koksbang, J. Barker, H. Shi, and M.Y. Saïdi, Solid State Ionics,
84 (1996) P.1.
14. A. Manthiram and J. Kim, Chem. Mater., 10 (1998) P.2895.
38
15. D. Abraham, presentation at CMM-MRL-UIUC, 28 Feb. 2001.
16. T. Ohzuku and A. Ueda, Solid State Ionics, 69 (1994) P.201.
17. M.M. Thackeray, Prog. Solid. St. Chem., 25 (1997) P.1.
18. H. Berg, Comprehensive Summaries of Uppsala Dissertations from

the Faculty of Science and Technology, P.485, Uppsala, 1999.
19. K. Kanamura, S. Shiraishi, H.T akezawa, and Z. Takehara, Chem.

Mater., 9 (1997) P.1797.
20. B.E. Conway, Electrochemical Supercapacitors, Klewer Academic

Plenum Publishers Chapter 7, P.125 (1999)
21. A.S. Fialkov, Russian J Electrochem., 36, 4, (2000) P.345.
22. M. Ue, A.Marakami and S.Nakamura, J. Electrochem. Soc., 149,

10, (2002) P.A1385.
23. M. Ue, M. Takeda, A. Toriumi, A. Kominato, R. Higiwara and Y.

Ito, J. Electrochem. Soc., 150, 4, (2003) P.A499.
24. Y.J. Kim, Y. Matsuzawa, S. Ozaki, et al, J. Electrochem. Soc., 152,

4, (2005) P. E135.
39
Chapter-2
LITERATURE REVIEW
40
2. Literature review
2.1. Review on carbon electrodes
The concept of the double layer have been studied by chemists since
the 19th century when von Helmholtz first developed and modeled the
double layer concept in investigations on colloidal suspensions [1]. This
work was subsequently extended to the surface of metal electrodes in the
late 19th and early- 20th centuries [2–6]. In 1957, the practical use of a
double-layer capacitor, for the storage of electrical charge, was demonstrated
and patented by General Electric [7]. This early patent utilized crude porous
carbon electrodes in an aqueous electrolyte. Not until the granting of a patent
to SOHIO in 1966 [8] was it acknowledged that these devices actually store
energy in the electrical double-layer, at the interphase between electrode and
solution. The first commercial double-layer supercapacitors originated from
SOHIO [9] who went on to patent a disc-shaped device that consisted of
carbon paste electrodes, formed by soaking porous carbon in an electrolyte
separated by an ion-permeable separator [10]. SOHIO also utilized
nonaqueous electrolytes in their early devices, but, a lack of sales saw them
license their technology to NEC in 1971; who further developed and
successfully marketed double-layer supercapacitors, primarily for memory
backup applications [11]. These early devices typically had a low voltage
and a high internal resistance [12]. By the 1980s a number of companies
were producing double-layer capacitors, e.g., Matsushita (Gold capacitor),
Elna (Dynacap) and PRI (PRI ultracapacitor), although the last-mentioned
incorporated relatively expensive metal oxide electrodes, primarily targeted
for military applications. Today, a number of high-performance EDLC
41
devices, based on porous carbons, are commercially available from a range
of manufacturers and distributors around the world [13]
The attraction of carbon as a supercapacitor electrode material arises

from a unique combination of chemical and physical properties, namely:
• High conductivity,
• High surface-area range (1 to 2000m2/g),
• Good corrosion resistance,
• High temperature stability,
• Controlled pore structure,
• Processability and compatibility in composite
materials,
• Relatively low cost.
In general terms, the first two of these properties are critical to the
construction of supercapacitor electrodes. As will be seen, the properties of
carbon allow both conductivity and surface area to be manipulated and
optimized. Such activities continue to be the subject of a considerable
amount of research. Prior to reviewing the results of this research, it is useful
first to consider in more detail other aspects of carbon, e.g., its structural
diversity and chemical behavior, so as to establish a better understanding of
the role of carbon materials in supercapacitors.
Carbon has four crystalline (ordered) allotropes: diamond (sp3
bonding), graphite (sp2), carbines (sp1) and fullerenes (‘distorted’ sp2). While
two carbon allotropes are naturally found on earth as minerals, namely,
42
natural graphite and diamond, the other forms of carbon are synthetic.
Carbon is considered unusual in the number of its allotropic structures and
the diversity of structural forms, as well as in its broad range of physical
properties [15, 16]. Due to the wide range of carbon materials, and to avoid
confusion, the term ‘carbon’ is typically used to describe the element rather
than its form. To describe a carbon-based material, it is best coupled with a
qualifier such as ‘carbon black’, ‘activated carbon’, ‘vitreous carbon’ and
others. A comprehensive guide to the terminology and description of carbon
solids, as used in the science and technology of carbon and graphite
materials, is available [17].
The majority of commercial carbons used today can be conveniently
described as ‘engineered carbons’. These are manufactured carbons that
have an amorphous structure with a more or less disordered microstructure
based on that of graphite [15]. Amorphous carbons can be considered as
sections of hexagonal carbon layers with very little order parallel to the
layers. The process of graphitization consists essentially of the ordering and
stacking of these layers and is generally achieved by high-temperature
treatment (>25000C). Between the extremes of amorphous carbon and
graphite, a wide variety of carbon materials can be prepared and their
properties tailored, to some extent, for specific applications.
The majority of carbon materials are derived from carbon rich organic
precursors by heat treatment in inert atmospheres (a process referred to as
carbonization). The ultimate properties of these carbons are dependent on a
number of critical factors, e.g., the carbon precursor, its dominant
aggregation state during carbonization (i.e., gas, liquid or solid), processing
conditions, and the structural and textural features of the products [18].
43
Summaries of the key processing conditions that lead to specific carbon
products and their features are outlined in Table 3.
It is usually anticipated that the capacitance of a porous carbon
(expressed in F/g) will be proportional to its available surface-area (in m2/g).
Whilst this relationship is sometimes observed [25, 21], in practice it usually
represents an oversimplification [14, 22, 23]. The major factors that
contribute to what is often a complex (non-linear) relationship are
1. Assumptions in the measurement of electrode surface-area

2. Variations in the specific capacitance of carbons with differing
morphology;
3. Variations in surface chemistry (e.g., wettability and
pseudocapacitive contributions discussed above);
4. Variations in the conditions under which carbon capacitance is
measured.
Most notably, the double-layer capacitance of the edge orientation of

graphite is reported to be an order of magnitude higher than that of the basal
layer [20, 24]. One determinant of specific double-layer capacitance could
therefore be the relative density of edge and basal plane graphitic structures
in carbon materials. Carbons with a higher percentage of edge orientations
(i.e., high Lc/La ratio) could be expected to exhibit a higher capacitance.
2.2. Review on electrolytes
Most compositions of lithium electrolytes are based on solutions of

one or more lithium salts in mixtures of two or more solvents, and single-
44
solvent formulations are very rare, if there are any. The rationale behind this
mixed solvent formulation is that the diverse and often contradicting
requirements of battery applications can hardly be met by any individual
compound, for example, high fluidity versus high dielectric constant;
therefore, solvents of very different physical and chemical natures are often
used together to perform various functions simultaneously. A mixture of
salts, on the other hand, is usually not used, because anion choice is usually
limited, and performance advantages or improvements are not readily
demonstrated.
In accordance with the basic requirements for electrolytes, an ideal
electrolyte solvent should meet the following minimal criteria
1. It should be able to dissolve salts to sufficient concentration. In

other words, it should have a high dielectric constant (ε).
2. It should be fluid (low viscosity), so that facile ion transport can
occur.
3. It should remain inert to all cell components, especially the
charged surfaces of the cathode and the anode, during cell
operation.
4. It should remain liquid in a wide temperature range. In other
words, its melting point (Tm) should be low and its boiling point
(Tb) high.
5. It should also be safe (high flash point Tf), nontoxic, and
economical.
For lithium-based batteries, the active nature of the strongly reducing

anodes (lithium metal or the highly lithiated carbon) and the strongly
45
oxidizing cathodes (transition metal based oxides) rules out the use of any
solvents that have active protons despite their excellent power in solvating
salts, because the reduction of such protons and/or the oxidation of the
corresponding anions generally occurs within 2.0- 4.0 V versus Li, while the
charged potentials of the anode and the cathode in the current rechargeable
lithium devices average 0.0-0.2 V and 3.0-4.5 V, respectively. On the other
hand, the nonaqueous compounds that qualify as electrolyte solvents must be
able to dissolve sufficient amounts of lithium salt; therefore, only those with
polar groups such as carbonyl, nitrile, sulfonyl, and ether-linkage (-O-) merit
consideration.
Since the inception of nonaqueous electrolytes, a wide spectrum of
polar solvents has been investigated, and the majority of them fall into either
one of the following families: organic esters and ethers.
An ideal electrolyte solute for ambient rechargeable lithium batteries
should meet the following minimal requirements
1. It should be able to completely dissolve and dissociate in the

nonaqueous media, and the solvated ions (especially lithium
cation) should be able to move in the media with high mobility.
2. The anion should be stable against oxidative decomposition at the
cathode.
3. The anion should be inert to electrolyte solvents.
4. Both the anion and the cation should remain inert toward the other
cell components such as separator, electrode substrate, and cell
packaging materials.
46
5. The anion should be nontoxic and remain stable against thermally
induced reactions with electrolyte solvents and other cell
components.
These salts include lithium perchlorate (LiClO4) and various lithium

borates, arsenates, phosphates, and antimonates, LiMXn (where M = B or
As, P, and Sb and n = 4 or 6, respectively).
2.3. Review on lithium compound electrodes
An insertion compound is a solid host network incorporating guest

ions. It has two specific properties which makes it different from a normal
solid structure: the guest ions are mobile between sites in the host network,
and the guest-ions can be removed from or added to the host network, thus
varying the guest-ion concentration. An insertion compound is an ionic and
electronic conductor, and the uptake or release of electrons compensates for
a change in guest-ion concentration. In Li-ion batteries, Li+ is the guest ion
and the host network comprises transition-metal-oxides (TMO’s), other
transition metal- chalcogenides (sulphides, selenides, or tellurides) or
transition-metal salts with oxoanions (e.g. phosphate, sulphate or arsenate).
For transition-metal oxides and other chalcogenides, positive guests
(like Li+) occupy sites surrounded by negative oxygen or chalcogen ions.
The guest ions strive to stay as far away as possible from the positive
transition-metal ions. The sites available to the Li-ion are determined by the
host structure. The first experimental investigation of a lithium insertion
compound was on the LixTiS2 structure [12]. It has later been established
that TMO’s are more attractive candidates for insertion electrodes [24]. This
47
is mainly due to their higher potential vs. Li/Li+ giving a high specific
energy and their excellent reversibility.
The term “intercalation” is sometimes used in the literature; it implies
a special case where “insertion” occurs into a layered host matrix, which
retains its structural integrity during the intercalation process.
The simplest and most studied insertion-compound structures contain
close-packed arrays of oxygen with the transition-metal (M) atoms
occupying half of the octahedral sites. These compounds are either layered
(LiMO2) or framework (LiM2O4) type. The ideal properties for an insertion
electrode in a Li-ion cell are [25, 26]
1. Large ∆G for the total cell reaction to provide a high cell voltage.
Limited change in ∆G over the useful range of inserted Li-ions to
ensure a stable operating voltage.
2. Minimal changes in the host network to ensure good reversibility.
3. Light host structure that is able to accommodate a significant
amount of Li to provide a high capacity.
4. Good electronic and ionic conductivity to provide high rate
capability.
5. Chemically and structurally stable over the whole voltage range
and insoluble in the electrolyte.
6. Inexpensive and non-toxic.
7. Low oxidation potential for a fully charged positive electrode (high
voltage vs. Li/Li+); high oxidation potential for a fully charged
negative electrode.
48
2.4. Review on hybrid supercapacitors
Hybrid electrochemical supercapacitors which consist of a battery-

type electrode and a capacitor-type electrode offer the advantages of both
supercapacitors (rate, cycle life) and the advanced batteries (energy density).
It shows higher energy density and the same time maintain the extended
cycle life and fast charge capability. Supercapacitors coupled with batteries
and fuel cells are considered as the most promising mid-term and long-term
solutions for low- and zero-emission transport vehicles. It has been rapidly
becoming the state-of-art of the energy storage devices. For example, in
AC/KOH/ Ni(OH)2 system [32], OH- in the electrolyte will transport to the
Ni(OH)2 cathode to form NiOOH, and K+ will drift to the carbon anode to
adsorb; in the Li4Ti5O12/LiPF6 ECDMC/ AC system [33], simultaneous with
the intercalation reaction of cation of Li-ion in the Li4Ti5O12 negative
electrode, anion of PF6- reversibly adsorbs/de-adsorbs on the surface of AC
positive electrode. Recently, we developed a new concept hybrid
electrochemical supercapacitor in which lithium intercalated compound
spinel structure LiMn2O4 was used as a positive electrode in combination
with an activated carbon negative electrode in a Li2SO4 aqueous electrolyte.
The new state-of-the-art hybrid aqueous supercapacitor technology
overcomes the drawbacks of electrolyte depletion during charge process of
conventional hybrid supercapacitors. It showed increased energy density,
maintained excellent cycling life, and also solved the major problems of
poor cycling life of lithium-ion battery electrode materials in aqueous
electrolyte [34].
49
References
1. H. von Helmholtz, Ann. Phys. (Leipzig) 89 (1853) 211.
2. G. Gouy, J. Phys. 9 (1910) 457.
3. D.L. Chapman, Phil. Mag. 25 (1913) 475.
4. O. Stern, Zeit. Elektrochem. 30 (1924) 508.
5. D.C. Grahame, Chem. Rev. 41 (1947) 441.
6. J.O. Bockris, M.A. Devanathan, K. Muller, Proc. R. Soc. A274

(1963)55.
7. H.I. Becker, Low voltage electrolytic capacitor, United States

Patent2,800,616 (1957).
8. R.A. Rightmire, Electrical energy storage apparatus, United States

Patent 3,288,641 (1966).
9. D.L. Boos, S.D. Argade, International Seminar on Double Layer

Supercapacitors and Similar Energy Storage Devices, Florida
Educational Seminars, Deerfield Beach, FL, 1991, p. 1.
10. D.L. Boos, Electrolytic capacitor having carbon paste electrodes,

United States Patent 3,536,963 (1970).
50
11. M. Endo, T. Takeda, Y.J. Kim, K. Koshiba, K. Ishii, Carbon Sci.
1(2001) 117.
12. M.F. Rose, Proceedings of the 33rd International Power Sources

Symposium, Pennington, NJ, 1988, p. 572.
13. A.M. Namisnyk, B.E. Thesis, University of Technology, Sydney,

Australia, 2003.
14. D. Qu, H. Shi, J. Power Sources 74 (1998) 99.
15. B. McEnaney, T.D. Burchell (Eds.), Carbon Materials for Advanced

Technologies, Pergamon, 1999, p. 1.
16. H.O. Pierson, Handbook of Carbon, Graphite, Diamond and

Fullerenes, Noyes Publications, NJ, USA, 1993.
17. E. Fitzer, K.-H. Köchling, H.P. Boehm, H. Marsh, Pure Appl.

Chem.67 (1995) 473.
18. M. Inagaki, L.R. Radovic, Carbon 40 (2002) 2263.
19. R.C. Bansal, J.B. Donnet, F. Stoeckli, Active Carbon, Marcel

Dekker, New York, 1988 (Chapter 2).
20. D. Qu, J. Power Sources 109 (2002) 403.
51
21. A. Yoshida, S. Nonaka, I. Aoki, A. Nishino, J. Power Sources
60(1996) 213.
22. S. Shiraishi, H. Kurihara, A. Oya, Carbon Sci. 1 (2001) 133.
23. M. Endo, Y.J. Kim, T. Takeda, T.H.T. Maeda, K. Koshiba, H. Hara,

M.S. Dresselhaus, J. Electrochem. Soc. 148 (2001) A1135–A1140.
24. R.L. McCreery, K.K. Cline, P.T. Kissinger, W.R. Heineman

(Eds.),Laboratory Techniques in Electroanalytical Chemistry, 2nd
ed., Marcel Dekker, New York, 1995, p. 293.
25. D. Lozano-Castelló, D. Cazorla-Amorós, A. Linares-Solano,

S.Shiraishi, H. Kurihara, A. Oya, Carbon 41 (2003) 1765.
26. Ue, M. J. Electrochem. Soc. 1995, 142, 2577.
27. Ravdel, B.; Abraham, K. M.; Gitzendanner, R.; Marsh, C.Extended

Abstracts of the 200th Electrochemical Society Meeting,San
Francisco, CA, Sept 2-7, 2001; Abstract No. 97; Electrochemical
Society: Pennington, NJ.
28. Xu, W.; Angell, C. A. Electrochem. Solid State Lett. 2001, 4, E1.
29. Hossain, S. Handbook of Batteries, 2nd ed.; Linden, D.,

Ed.;McGraw-Hill: New York, 1995; Chapter 36.
52
30. Schmidt, M.; Heider, U.; Kuehner, A.; Oesten, R.; Jungnitz,
M.;Ignat’ev, N.; Sartori, P. J. Power Sources 2001, 97/98, 557.
31. Walker, C. W.; Cox, J. D.; Salomon, M. J. Electrochem. Soc. 1996,

143, L80.
32. S.M. Lipka, D.E. Reisner, J. Dai, R. Cepulis, in: Proceedings of

the11nternational Seminar on Double Layer Capacitors, Florida
Educational Seminars Inc., 2001.
33. G.G. Amatucci, F. Badway, A.D. Pasquier, T. Zheng, J.

Electrochem.Soc. 148 (2001) A930.
34. Y.Y. Xia, Y.G. Wang, A hybrid lithium-ion aqueous cell, Patent CN
200510025269.6.
53
Chapter-3
SCOPE &
OBJECTIVE
54
3. Scope and objective
This project aims at developing a Hybrid supercapacitor based on

LiCo1-xAlxO2 (x = 0, 0.2, 0.4 and 0.6) cathode materials synthesized by soft
combustion method from their respective nitrate precursors using Glycine as
fuel. Carbon NanoFoam has been used as anode material with Non-
aqueous electrolyte to characterize their physical and electrochemical
properties to be used for hybrid supercapacitors.
The commercially available carbon based supercapacitors and
pseudocapacitors based on metal oxides have many disadvantages say, high
voltages cannot be reached, low energy densities and poor charge retention.
All these problems have been addressed in this work.
In the case of conventional supercapacitors or pseudocapacitors the
power obtained is only due to the charge separation and no redox behavior
may be observed and as a result they may have high power densities but
their energy density value is too low. This problem has been eliminated in
this work by replacing one of electrodes with a battery material. Thus with
the use of battery material, the charge retention property and the energy
density value may be improved effectively.
Hence the main objectives of our project is to
Synthesis LiCoO2 and to dope with Aluminium

Fabricate hybrid supercapacitors
Study its physical and electrochemical characterizations
55
Although variety of battery materials are available, we have chosen
LiCoO2 because of its advantages like high energy density, ease of synthesis
etc. and aluminium to dope with the parent material. The reason for
choosing the above material for this study is due to its various advantages
which may be listed as follows.
3.1. Advantages of hybrid supercapacitors
In supercapacitor two symmetric capacitors are connected in series

and the total capacitance is halved.
1/Ctotal = 1/C + 1/C
Ctotal = C/2.
But in a hybrid supercapacitor, one of the electrodes is replaced by a

battery electrode. So we can get the total capacitance of the single capacitor
electrode with the added advantages of battery electrode.
Electrochemical capacitors are currently receiving great attention for
their use as energy-storage devices in high-power applications with their
potential applications ranging from mobile devices to electric vehicles (EV).
It has virtually unlimited cycle life, but modest energy densities. At the other
end of the spectrum, Li-ion batteries benefit from the highest energy densities,
suffer limited cycle life and lack the ability to safely accept the fast charging
without Li metal deposition.
To merge the advantages of both systems, Amatucci et al [1] invented
a new class of nonaqueous hybrid devices which utilizes Li-intercalation
56
anode and an acetonitrile-LiBF4 electrolyte, combined with an activated
carbon double-layer cathode. The combined effect of a higher output voltage
and an anode of greater specific capacity results in higher energy densities
than carbon/carbon supercapacitors, while maintaining a high power density
and robustness.
Recently, Xia et al [2] developed new concept hybrid electrochemical
supercapacitors in which a lithium intercalated compound was used as a
positive electrode in combination with an activated carbon negative
electrode in a Li2SO4 aqueous electrolyte. The new state-of-the-art hybrid
aqueous supercapacitor technology overcomes the drawbacks of electrolyte
depletion during charge process of conventional hybrid supercapacitors. It
showed increased energy density, maintained excellent cycling life, and also
solved the major problems of poor cycling life of lithium-ion battery
electrode materials in aqueous electrolyte.
In the present work, we reported the composition and the
electrochemical performance of such type hybrid supercapacitors based on
Pure and doped LiMn2O4 cathode material.
3.2. Advantages of LiCoO2
LiCoO2 has a layered structure where lithium and transition metal

cations occupy alternate layers of octahedral sites in a distorted cubic close-
packed oxygen ion lattice. The synthesis of LiCoO2 on industrial scale is
easier than LiNiO2. It also shows better reversibility, long cycle life and very
high energy density. The substance has been doped with Al to increase the
potential window.
57
The layered structure of LiCoO2 is clearly represented in
Fig 3.1.
Fig 3.1: Layered structure of LiCoO2
3.3. Advantages of CNF
Carbon Nano Foam is having the following positive properties

compared to other carbons.
High surface area (1500 m2/g)

Low electrical resistance
No participation in Faradaic reactions at the applied
voltage
High capacity (100 - 200 F/g)
Unlike Activated Carbon, CNF combine high surface
area with high bulk density to give large capacitance
values
58
3.4. Advantages of non-aqueous electrolyte
The reason for this inability to reach higher voltages arises from the
use of aqueous electrolyte because at voltages higher than 1.2V, problems of
H2 and O2 evolution occur. This problem has been solved by the replacement
of aqueous electrolyte with non-aqueous electrolyte where the problem of
hydrogen and oxygen evolution at higher voltages may easily be eliminated.
The non-aqueous electrolyte used in this present study is 1M LiClO4 in
Ethylene carbonate-Propylene Carbonate.
References
1. G.G.Amatucci, F.Badway, A.D.Pasquier, T.Zheng, J.Electrochem.

Soc. 148 (2001) P.A930.
2. Y.Y.Xia, T.Sakai, T.Fujieda, X.Q.Yang, X.Su, Z.F.Ma, J.McBreen,

M.Yoshio, J. Electrochem. Soc. 148 (2001) P.A723.
59
Chapter-4
EXPERIMENTAL
60
4. Experimental
4.1. Synthesis of cathode material
4.1.1. Existing methodologies for the synthesis of cathode materials
A number of methods are available to synthesize cathode materials for

their use in rechargeable lithium batteries and in hybrid supercapacitors
involving Li intercalated compounds as one of the electrodes. Of all, the
conventional solid - state fusion method is the one which has gained a wide
popularity after Sony’s first Li-ion cell with LiCoO2 as the active material.
But the very same method in view of homogeneity and time requirement to
end up with the product has led to the blooming of various other
technologies such as sol gel, combustion and precursor methods.
The general methods of synthesis may be grouped under the following
three categories:
Solid-state synthesis
Sol-gel method
Soft combustion process
4.1.2. Need to identify suitable synthesis methods
Literature is replete with the methods of synthesis of these materials

that employ various precursors and heating procedures with variation in
temperature, reaction time, atmosphere, etc. The standard approach towards
synthesizing the cathode samples namely, the solid solution method usually
required a long heating time and high temperature. Firing at high
61
temperature includes crystalline growth which causes adverse effects on the
electrochemistry of the materials. In other words, the formation of large
crystallites tends to lower the kinetics of diffusion. By contrast, smaller
particles result in better cyclability, charge retention, and smaller IR drop.
Therefore, particle-size has a direct influence on the electrochemical
performance of the cell. High temperature processing may lead to Li loss
and there by affects the stoichiometry and structural characteristics of the
compound.
Hence it is essential to identify an ideal methodology that can result in
the formation of stoichiometric compounds with good control over
chemistry, purity, morphology etc., of the crystals. Generally, the electrode
materials are synthesized in nano and micron levels. Nano structured
electrode materials can either improve the energy density of batteries or
enhance the rate capability of Lithium–based batteries. But the synthesis of
nano structured materials requires stringent conditions. Hence we opted for
the synthesis of novel electrode materials in micron level. We have chosen
soft combustion method and our choice may be justified as follows:
4.1.3. Soft combustion method
Combustion or self propagating high-temperature synthesis is a

versatile method used for the synthesis of a variety of solids. The method
makes use of a highly exothermic reaction between the reactants to produce
a flame due to spontaneous combustion which then yields the desired
product or its precursor in finely divided form. Borides, carbides, oxides,
chalcogenides and other metal derivatives have been prepared by this
method and the topic has been reviewed recently by Merzhanov [1]. In order
62
for the combustion to occur, one has to ensure that the initial mixture of
reactants is highly dispersed and has high chemical energy. For example,
one may add a fuel and an oxidizer when preparing oxides by the
combustion method, both these additives being removed during combustion
to yield only the product or its precursor. Thus, one can take a mixture of
nitrates (oxidizer) of the desired metals along with a fuel (e.g. hydrazine,
glycine or urea) in solution, evaporate the solution to dryness and heat the
resulting solid to around 423K to obtain spontaneous combustion, yielding
an oxidic product in fine particulate form. Even if the desired product is not
formed immediately after combustion, the fine particulate nature of the
product facilitates its formation on further heating. In order to carry out
combustion synthesis, the powdered mixture of reactants (0.1 – 100 µm
particle size) is generally placed in an appropriate gas medium which favors
an exothermic reaction on ignition. The combustion temperature is anywhere
between 1500 and 3500K, depending on the reaction. Reaction times are
very short since the desired product results soon after the combustion. The
gas medium is not always necessary. This is so in the synthesis of borides,
silicides and carbides where the elements are quite stable at high
temperatures (e.g. Ti + 2B – TiB2). Combustion in a nitrogen atmosphere
yields nitrides. Nitrides of various metals have been prepared in this manner.
Azides have been used as sources of nitrogen. The following are some
typical combustion reactions
MoO3 + 2SiO2+ 7Mg ( MoSi2+7MgO)

WO3+C+2Al ( WC+Al2O3)
TiO2+B2O3+5Mg ( TiB2+ 5MgO)
63
Recently, MoS2 and other refractories have been prepared from
halides [2].
Use of the combustion method in an atmosphere of air or oxygen to
prepare complex metal oxides seems obvious. In the last three to four years,
a variety of oxides have been prepared using nitrate mixtures with a fuel
such as glycine or urea [3]. It seems that almost any ternary or quaternary
oxide can be prepared by this method [4]. All the superconducting cuprates
have been prepared by this method, although the resulting products in fine
particulate form have to be heated to an appropriate high temperature in a
desired atmosphere to obtain the final cuprate. The typical materials
prepared by the combustion method are listed in table 4.1 [5].
Table 4.1: Typical materials prepared by combustion method.

Oxides BaTiO3, LiNbO3, PbMoO4,
Bi4Ti3O12, BaFe12O19, YBa2Cu3O7
Carbides TiC, Mo2C, NbC
Borides TiB2, CrB2, MoB2, FeB
Silicides MoSiO2, TiS2, ZrSi2
Phosphides NbP, MnP, TiP
Chalcogenides WS2, MoS2, MoSe2, TaS2, LaTaS3
Hydrides TiH3, NdH2
64
The important advantages of soft combustion method are listed
below
Single step process with good product yield.
Short processing time at moderate temperature
High chemical homogeneity
Mono-dispersed particles of submicron size
Large surface area which leads to better electrochemical
performance
4.1.4. Synthesis procedure
The LiDxM1-xO2 (x =0, 0.2, 0.4 and 0.6; M – Co; D – Al) active
materials were synthesized by adopting soft combustion method.
Stoichiometric proportions of respective high purity metal nitrates (Merck,
India) were dissolved in distilled water. The details of composition are
shown in Table 4.2 based on the following reaction.
LiNO3 + (1-x) Co(NO3)2.6H2O + x Al(NO3)2.9H2O LiCo1-xAlxO2
The contents in the beaker were allowed to cook and a calculated

quantity of glycine was added as a fuel. The solution obtained initially was
stirred well using a magnetic stirrer and then heat treated at 1000C for 6 h.
The product obtained in this stage was ground to yield finer particles and
was subjected to TG/DTA analysis to know the stability of the compound
with increase in temperature.
65
Table 4.2: Composition for synthesis of LiCo(1-x)AlxO2 (x = 0, 0.2, 0.4, 0.6)
Requirement
Precursor
X=0 X=0.2 X=0.4 X=0.6
LiNO3 13.8g 13.8 g 13.8g 13.8
Al(NO3)2.9H2O 0 15 g 30g 45g
Co(NO3)2.6H2O 58.2g 46.56 g 34.92g 23.28g
Glycine ( C2H5NO2) 30g 30 g 30g 30g
Distilled Water 100ml 100 ml 100ml 100ml
4.1.5. Flow chart for synthesis of LiCoO2
Weighing of required chemicals
Dissolve in 100ml distilled water
Stir well at 600C
Heat the mixture at 1000C for 6 hours
Product is formed following a soft combustion
66
4.1.6. Annealing
The temperature for annealing the sample prepared can be found by

thermo gravimetric analysis. The temperature was found to be around
8500C. Therefore the samples are annealed at 8500C for duration of 4 hours.
After annealing the samples are packed separately and given for physical
characterization.
4.2. Physical characterization techniques
TG/DTA is used to find the drying temperature. The degree of cation

ordering and local cation structure are identified through FTIR studies. XRD
patterns of the synthesized materials are used to identify the formation,
purity and crystallinity of the samples individually. SEM images indicate the
surface morphology possessed by the synthesized powders.
4.2.1. Thermal analysis
4.2.1.1. Thermo-gravimetric analysis
TGA is generally used to find the optimum temperature ranges for

drying a sample to remove the moisture and impurities from it. Here the
apparatus used is having a thermo balance. In this analysis the weight of a
sample is followed over a period of time while its temperature is increased
linearly. A simple layout of TGA apparatus is shown in Fig 4.1.
67
Fig 4.1: Diagram of Thermo Gravimetric Analyzer
TGA has been conducted for all four samples in the instrument SDT
Q600 V8.2 Build 100 at a heating rate of 200C per minute in Nitrogen
atmosphere.
4.2.1.2. Differential thermal analysis
In this analysis phase transitions or chemical reactions are followed

through observation of heat absorbed or liberated. It is especially suited to
study structural changes within a solid at elevated temperatures, where few
other methods are available. The temperature difference between a sample
68
and an inert reference material is monitored while both are subjected to a
linearly increasing environmental temperature. A typical schematic
representation of DTA apparatus is shown in Fig 4.2.
Fig 4.2: Construction of Differential Thermal Analyzer
With constant heating, any transition or thermally induced reaction in

the sample will be recorded as a peak or dip in an otherwise straight line. An
endothermic process will cause the thermocouple junction in the sample to
lag behind the junction in the reference material, and hence develop a
voltage, whereas an exothermic event will produce a voltage of opposite
sign. It is customary to plot exotherms upward and endotherms downward.
The usual mode of operation is to supply heat to the samples, and therefore
endothermic events are more likely to occur than exothermic. When an
exotherm does occur, it is often caused by a secondary process. DTA has
69
been conducted for all our four samples in the instrument SDT Q600 V8.2
Build 100 at a heating rate of 200C per minute in Nitrogen atmosphere.
4.2.2. Fourier transform infra red spectroscopy
The FTIR spectroscopy deals with the study of the interaction of

matter with infrared radiation. The absorption by a sample requires that the
energy content of radiation should correspond to the energy difference
between the vibrational states; there should be strong coupling reaction
between the sample and the radiation. This coupling interaction takes place
only if there is a change in dipole moment during the absorption process.
If there is no change in dipole moment during the absorption process,
there will be no coupling interaction between the sample molecules and
radiation, and therefore no absorption is possible, even if the first condition
is satisfied.
Radiation in the near-IR region (4000-12,500 cm-1) excites harmonics
of molecular vibrations as well as low energy electronic transitions in
molecules. Generally employed source is a Quartz-enveloped tungsten-
halogen lamp, with detection by photomultiplier or photodiodes. The mid-IR
region (200-4000 cm-1) is the one where most stretching and bending
fundamental vibrations of molecules occur.
Radiation source is Nernst glowers or globars and detectors are
thermocouples or photoconductive materials like HgCdTe or InSb. The far-
IR (10-200 cm-1) is where rotational in gaseous molecules and lattice modes
are observed. A simple layout of FTIR spectrometer is shown in Fig 4.3.
70
Fig 4.3: Layout of FTIR spectrometer
Radiation source is high pressure mercury arc and doped-germanium

bolometers are useful detectors. Solids can be observed directly as thin
sections; as mulls in mineral or fluorocarbon oils; as finely ground
dispersion in discs of an IR-transparent salt such as CCl4 or CS2. The
usefulness of water is limited by its strong and broad IR-absorptions.
Infrared spectra are usually plotted as percentage transmittance (% T) or
absorbance (A) on a scale, linear in wave numbers (v). Transmittance is the
71
ratio of the intensity of radiation transmitted by the sample (I) to the incident
sample (I0), expressed as a percentage, so that T=100(I/I0) and, T and A are
related as
A=log10 (I0/I) =log10 (100/T) =2-log10T
By employing a mathematical procedure called as the “Fourier

Transform (FT)”, the desired spectrum i.e. the source intensity as a function
of wave number can be obtained.
FTIR spectra were recorded employing a Perkin-Elmer paragon-500
FTIR spectrophotometer using KBr pellets in the region of 400-3500 cm-1.
4.2.3. X-ray diffraction
When X-rays interact with a crystalline substance (phase), one gets a

diffraction pattern. In 1919 A.W.Hull gave a paper titled, “A New Method
of Chemical Analysis”. Here he pointed out that “Every crystalline
substance gives a pattern; the same substance always gives the same pattern;
and in a mixture of substances each produces its pattern independently of the
others”. The X-ray diffraction pattern of a pure substance is, therefore, like a
fingerprint of the substance. The powder diffraction method is thus ideally
suited for characterization and identification of polycrystalline phases.
Today for about 50,000 inorganic and 25,000 organic single component,
crystalline phases, diffraction patterns have been collected and stored on
magnetic or optical media as standards.
The main use of powder diffraction is to identify components in a
sample by a search/match procedure. Furthermore, the areas under the peak
are related to the amount of each phase present in the sample. In crystalline
72
substances the atoms are arranged in a regular pattern, and there is as
smallest volume element that by repetition in three dimensions describes the
crystal. For example we can describe a wall by the shape and orientation of a
single brick. This smallest volume element is called a unit cell. The
dimensions of the unit cell are described by three axes a, b, c and the angles
between them alpha, beta, and gamma.
An electron in an alternating electromagnetic field will oscillate with
the same frequency as the field. When an X-ray beam hits an atom, the
electrons around the atom start to oscillate with the same frequency as the
incoming beam. In almost all directions we will have destructive
interference, that is, the combining waves are out of phase and there is no
resultant energy leaving the solid sample. However the atoms in a crystal are
arranged in a regular pattern, and in a very few directions we will have
constructive interference. The waves will be in phase and there will be well
defined X-ray beams leaving the sample at various directions. Hence, a
diffracted beam may be described as a beam composed of a large number of
scattered rays mutually reinforcing one another. There is a definite relation
between the angle of diffraction (θ), wavelength of X-radiation (λ and the
inter-atomic spacing (d) of the crystal; popularly known as the “Bragg’s
law” which is
nλ=2d sin θ.
This model is complex to handle mathematically, and in day to day
work we talk about X-ray reflections from a series of parallel planes inside
the crystal. The orientation and interplanar spacing of these planes are
defined by the three integers h, k, l called indices. A given set of planes with
indices h, k, l cut the a-axis of the unit cell in h sections, the b axis in k
sections and the c axis in l sections. A zero indicates that the planes are
73
parallel to the corresponding axis. e.g. the (2, 2, 0) planes cut the a– and the
b– axes in half, but are parallel to the c– axis.
Phase characterization was done by powder X-Ray diffraction
technique on a Philips 1830 X-Ray diffractometer using Ni filtered Cu-Kα
radiation (λ=1.5406) in the 2Ө range of 10-120° at a scan rate of 0.1˚/s.
4.3. Cell fabrication
After the completion of physical characterizations, a cell has to be

fabricated to proceed with electro-chemical characterization. The
constituents of a cell may be listed as follows:
Current collector - Mild steel

Positive material - LiCo(1-x)AlxO2 (x = 0, 0.2, 0.4, 0.6)
Negative material - Carbon Nano Foam
Binder - N- Methyl Pyrrolidine
Separator - Polypropylene
Electrolyte - 1M LiClO4 in EC-PC
4.3.1. Composition for positive electrode
LiCo(1-x)AlxO2 (x = 0, 0.2, 0.4, 0.6)-------- 80%

CNF------------------------------------------- 15%
Binder----------------------------------------- 5%
A small amount of CNF is added to the positive electrode to increase

its conductivity.
74
4.3.2. Composition for negative electrode
CNF--------------------------------------------- 95%
Binder------------------------------------------- 5%
4.3.3. Steps involved in cell fabrication
Initial polishing and weighing of the current collectors
Two current collector samples, each of size 1cm2 are taken, polished
manually and weighed initially to fabricate a single cell.
Pasting of electrode materials
The electrode materials are weighed based on the above composition

and ground well uniformly in a mortar and pestle which is shown on Fig 4.4.
Fig 4.4: Binder, Spatula, Mortar and Pestle.
75
After grinding the electrode materials, NMP binder is added and the
powder was made into a paste. This paste was applied on the polished
surface of the current collector (MS).
Drying the pasted electrode
The electrodes were then dried in an oven at 2000C for 30 minutes to

allow the binder material to evaporate and cooled to room temperature. It is
weighed finally to calculate the weight of active material present in it. A
single electrode after taken out from the oven is shown in Fig 4.5.
Fig 4.5: A dried single electrode
Fabrication of supercapacitor cell
Both positive and negative electrodes were prepared as above and

they are tied together using a nylon thread after keeping a polypropylene
separator in between. Care should be taken to avoid any contact between the
electrode materials. The pair of electrodes tied together is shown in the fig
4.6. Then the electrodes are dipped in a beaker containing EC-PC
electrolyte. A completely fabricated supercapacitor cell is shown in Fig 4.7.
76
Fig 4.6: Electrodes tied using Fig 4.7: A fully fabricated
nylon thread supercapacitor cell
4.4. Electrochemical characterization techniques
4.4.1. Cyclic voltammetry
Cyclic Voltammetry technique is used to determine the capacitance of

an electrochemical capacitor. An electrode-elctrolyte interface in the absence
of a redox couple is not a pure parallel-plate capacitor, it behaves rather like
one and a parallel-plate capacitor model is often adequate to describe
electrochemical systems. Use of this model allows us to learn about the
behavior of electrodes in the absence of a redox couple. For a simple parallel
plate capacitor, charge on the capacitor, Q, is proportional to the voltage
drop E, across the capacitor.
Q = CE …………...……………………………4.1
77
The proportionality constant C is the capacitance of the medium. The
simplest description of electrochemical capacitance is the Helmholtz model
given by:
…………………...................................4.2
Where ε is the dielectric constant of the material separating the

parallel plates, εo is the permittivity of free space, l is the separation between
the plates, and A is the area of the electrode. This model does not adequately
describe all electrochemical interfaces as the capacitance can depend on both
potential and the supporting electrolyte. Still it is a helpful construct.
Capacitance is a crucial factor in electrochemical experiments because
it gives rise to current during the charging of the capacitor. Rather logically
(and without imagination), we term this as charging current. To calculate the
magnitude of this current, we differentiate equation 4.1 with respect to t
assuming that the capacitance is constant
…………………...................................4.3
Recognizing that dQ/dt is an expression for current and dE/dt is the

potential scan rate ν, we obtain
……………………………………….4.4
From this very simple derivation, we have an expression for the

charging current at steady state when applying a ramping voltage. Thus by
78
measuring the charging current at a given scan rate, we can determine the
capacitance of the system. If there is no possibility for electron transfer
between the solution and the electrode (we don’t add a redox couple) this is
the only current that we will observe. Let’s now consider the very simple
cyclic voltammetry (no active redox couple present) experiment shown in
Fig 4.8. We apply the potential form shown in the figure. Initially, we have a
sharp rise in current because of a sharp change in the scan rate ν. The current
then reaches steady state as constantly varying the voltage. At reversal of the
scan rate, the current changes sign, and when we stop scanning, current goes
to zero.
Fig 4.8: Schematic explanation of a cyclic voltammetry experiment in the

absence of a redox couple.
4.4.2. Electrochemical impedance spectroscopy
Electrochemical Impedance Spectroscopy (EIS) is a characterization

technique where by a sinusoidal voltage wave of known amplitude and
frequency is passed through the test subject (usually a standard test cell).A
79
sine wave is utilized because it has a characteristic magnitude (E) and
frequency (ω)
e = E sin ωt …………………………….....…4.5
Where t is the indication of time. This voltage induces a flow of

current when it is applied to an electrochemical system. This current (I) can
be described as
i = I sin (ωt + θ) ……………………………....4.6
The sinusoidal wave is phase shifted (θ) depending on the nature of

the intrafacial region next to the test electrode. Conversion of the measured
current into a voltage allows for the comparison between the excitation and
resultant waveforms. The magnitude and phase differences can be measured
and compared resulting in two pieces of information.
Fig 4.9: Magnitude of the resultant Fig 4.10: Phase difference

sine wave as a function of frequency between the incident and resultant
for a representative standard test cell wave forms
with one layer of Celgard 2500.
80
The magnitude and phase shift can be alternately designated as the
real and imaginary impedances, ZI and ZII, respectively. The relationship
between the two sets is given by
2 2
|Z| = |E|/|I| = √ (ZI + ZII ) ……………….………..….4.7
and
tan θ = ZII/ZI …………………………………..4.8
The real impedance is measured in phase, and the imaginary

impedance is measured 90° out of phase with the excitation waveform
Fig 4.11: The real portion of the Fig 4.12: The imaginary portion
resultant wave form as a function of the resultant wave form as a
of frequency. function of frequency.
81
A convenient and largely accurate, model for a supercapacitor is a
simple Resistor-Capacitance series circuit. The resistance (R) portion of the
circuit affects only the magnitude of the resultant signal. No phase shift is
observed. Hence
ZI = R ……….……………………...….4.9
In contrast the capacitance (C) induces a phase shift of -90°. The

effect is frequency dependant and does not contribute to the real impedance.
Hence
ZII = 1/ (ωC) …………………………….…...4.10
The magnitude can be calculated by substituting equations 4.9 and 4.10
into 4.7, thus
2 2 2
|Z| = √ (R + 1/ (ω C )) …………………….....4.11
Similarly the phase angle can be calculated by substitution of

equations 4.9 and 4.10 into 4.8.
θ = arc tan (1/ωRC) …………………….…….4.12
The phase angle varies from 0° to -90° depending on the frequency.

This phase angle variation is indicative of the dominant circuit element. At
low frequencies the phase angle is -90° and is dominated by the
capacitance.
High frequencies are dominated by the resistance and have a phase
angle of 0°. The change between the phase angles are an analogue shift. At
82
a phase angle of 45° the resistance and capacitance are equally dominant.
The frequency dependant impedance can be written as
Z (ω) = R + (1/jωC) ……………………….….4.13
where the symbol j indicates √(-1)
The first phase of the characterization involved performing EIS as a

function of frequency. This gives data such as the Fig 4.13 and Fig4.14
shown below
Fig 4.13: The resistance of Fig 4.14: Capacitance

the resultant waveform as a the resultant waveform as a
.
function of frequency. function of frequency
. The most convenient form of these is the resistance

and capacitance data shown as an example in figures 4.13 and 4.14 above.
A frequency sweep is one method of utilizing the EIS. A second method
involves an EIS test at a fixed frequency. Frequency of 1 kHz was chosen,
83
because it is an industry standard for measuring equivalent series resistance
(ESR). It is generally considered that the phase angle is zero, or very closes
to zero, at this point. The voltage is changed in 0.25V increments, from 0V
bias to 2.5 volts. The experiment is continued as the voltage is ramped
back down to 0V bias and then back up to 2.5V. A voltage hold phase
preconditions the cell to the voltage that is being tested in the next step.
This phase extends for one minute and then the test runs for two minutes,
collecting 120 evenly spaced data points during this time. This small time
fame is the rationalization for the fact that the cell sees slightly higher then
the nominally accepted limit for a device of this configuration.
4.4.3. Galvanostatic charge-discharge cycle tests
This is used to evaluate performance of the supercapacitors. The

instrument Won-A-Tech WBCS 3000 was used for automatic
charge/discharge of supercapacitors. Here a charge/discharge current density
of 500µA/cm2 was used.
References
1. A.G. Merrzhanov, C.N.R. Rao (ed.) (1992) ‘chemistry of advanced

materials’, IUPAC 21st century monograph series, Blackwell,
oxford, p.19
2. M. Mohanrao, M. Jeyalakshmi, O.Schoff, U. Guth, Wulff, F. Scholz

(1999) Journel of Solid State Electrochemistry, P.17
84
3. P.R. Bonneau, R.F. Jarvis, Jr and R.B. Kaner (1991) Nature, P.510.
4. R. Mahesh, VA. Pavate, Om prakash and C.N.R. Rao (1992)

Superconductors Science and Technology, P.174.
5. W. LI, J.N. Reimers, J.R. Dahn (1993) Solid State Ionics, p.123.
85
Chapter-5
RESULTS &
DISCUSSIONS
86
5. Results and discussions
5.1. Thermal analysis
5.1.1. Thermo-gravimetric analysis
1.0
0.9
Weight fraction
0.8
0.7
0.6
LiCoO2
LiCo0.8Al0.2O2
0.5 LiCo0.6Al0.4O2
LiCo0.4Al0.6O2
0.4
0 200 400 600 800 1000 1200 1400
0
Temperature ( C)
Fig 5.1: TGA curves of base LiCoO2 and aluminium doped

Lithium Cobaltate.
In Fig 5.1, the initial weight drop from 300C-1500C is due to moisture
removal from the sample. And the subsequent weight loss from 1500C to
3000C corresponds to the elimination of organic compounds from the
samples. The weight drop observed in the temperature range of 3000C-5000C
is as a result of the reaction of unreacted precursors to give the final product.
The stabilization temperature for these samples mostly lay after
8000C. Hence the samples are heated at 8000C for 4 hours. It is also known
87
from the figure that when the aluminum substitution exceeds the fraction of
cobalt the decomposition is very low.
5.1.2. Differential thermal analysis
Fig 5.2 shows that all base and doped substances are having the
similar behavior in DTA performance, that involves the exothermic
reactions corresponding to the elimination of compounds listed above.
2.0
1.5
Temperaturedifference( C)
0
1.0
0.5
0.0
-0.5
LiCoO2
-1.0 LiCo0.8Al0.2O2
LiCo0.6Al0.4O2
-1.5 LiCo0.4Al0.6O2
-2.0
0 200 400 600 800 1000 1200
0
Temperature( C)
Fig 5.2: DTA curves of base LiCoO2 and aluminium doped

Lithium Cobaltate.
5.2. FTIR spectroscopy
Figs 5.3–5.6 show the FTIR spectrum of LiCoO2, LiCo0.8Al0.2O2,

LiCo0.6Al0.4O2, and LiCo0.4Al0.6O2 respectively. These data indicate the
88
formation of compressed CoO6 and LiO6 elongated octahedra. Upon sp
element substitution, the vibrational mode of LiO6 units observed in the far-
infrared region appears quite stable.
The systematic change in frequency of the high-wave number IR
bands as a function of Al doping is not surprising, while a blue shift is
expected with the increase of Al content. The intensity of the stretching
mode (Eu symmetry) located at 558 cm−1 increases significantly for y (Al) =
0.4, which compares with the shape of the IR feature at 510–570 cm−1 for
LiAlO2. These results show that, by doping, the local environment of lithium
ions surrounded by oxygen anions is not strongly affected and the CoO2
layer covalency increases slightly. For high level of Al substitution, the
broadening of the infrared peaks can be interpreted as an increase in CoO6
distortion due to the incorporation of Al3+ in the CoO2 layers. However,
because the stability of the LiO6 stretch, we can conclude that Al3+ cations
were not incorporated in the Li sites of the interlayer space.
100
80
%Transmittance
60
40
20
0
500 1000 1500 2000 2500 3000 3500
-1
Wave number (cm )
Fig 5.3: FTIR spectrum of LiCoO2
89
100
%Transmittance 80
60
40
20
0
500 1000 1500 2000 2500 3000 3500
-1
Wave number(cm )
Fig 5.4: FTIR spectrum of LiCo0.8Al0.2O2
100
80
%Transmittance
60
40
20
0
500 1000 1500 2000 2500 3000 3500
-1
Wave number(cm )
90
100
80
%Transmittance
60
40
20
0
500 1000 1500 2000 2500 3000 3500
-1
Wave number(cm )
5.3. X-ray diffraction
Fig 5.7 displays the XRD patterns of LiAlxCo1−xO2 (0.0 ≤ x ≤ 0.6)

oxides. These data show that most of the compounds are single phase when
obtained through careful selection of precursors. As the substitution of Al3+
for Co3+ ions occurs in the LiCoO2 rhombohedral structure, a solid solution
of lithium cobaltate and lithium aluminate is obtained for the LiAlxCo1−xO2
materials up to x = 0.6. The XRD patterns of the samples synthesized for
this study were indexed in the rhombohedral R3m space group. Miller
indices (h k l) are indexed in the hexagonal setting. No impurity phase was
detected in the XRD patterns.
91
(003)
(104)
(006)
LiCo0.4Al0.6O2
(101)
(012)
(107)
(108)
(105)
(110)
(113)
(201)
%intensity
LiCo0.6Al0.4O2
LiCo0.8Al0.2O2
LiCoO2
10 20 30 40 50 60 70 80 90 100
2 theta
Fig 5.7: XRD spectra of cathode materials
LiCo0.4Al0.6O2
LiCo0.6Al0.4O2
%Intensity
LiCo0.8Al0.2O2
LiCoO2
36 37 38 39 40
2 theta
Fig 5.8: XRD spectra of cathode materials
92
Fig5.8 shows the portions of XRD patterns (in the 2θ range from 35 to
410) from LiAlxCo1−xO2 for 0.0 ≤ x ≤ 0.6 illustrating the lattice parameter
shifts in the solid solution. As the aluminium content increases a broadening
of the diffraction peaks are observed. The (0 0 6) and (1 0 8) peaks shift
toward lower 2θ angles, resulting in a wider split of doublets corresponding
to the (0 0 6) (1 0 2) and (1 0 8) (1 1 0) Bragg lines compared with the native
oxide LiCoO2.
5.4. Cyclic voltammetry
The cyclic voltammetry experiments were carried out at various scan

rates in BAS 100A and BAS 100B instruments. In hybrid electrochemical
supercapacitors or double-layer capacitors, the cations and anions seperate
during the charge process. Charges stored at both electrodes should be
balanced and equal the charge of ions consumed from the electrolyte. The
electrolyte depletion problems limit greatly their energy density. In this
work, (LiCoO2/CNF) Li ions adsorb on the surface of the carbon nanofoam
electrode. The reverse process occurs during discharge. The Li ions transfer
from one electrode to another during the charge and discharge cycles. The
electrolyte mainly functions as the ionic conductor and is not consumed.
This new hybrid technology overcomes the drawbacks of electrolyte
depletion during the charge process of conventional hybrid supercapacitors
and it shows increased energy density and power density.
The CVs of as prepared LiCoO2 and CNF in electrolyte of 1M LiClO4
in EC:PC (50:50) at various scan rates are given in Fig.5.9. In order to
improve the electronic conductivity 15% of CNF was added to LiCoO2. The
93
Oxygen evolution potential was also investigated and occurred at 1.8V
which is higher than 1.3V as the pure LiMn2O4 electrode reported else where
[1].
The curves also reveal that the CNF electrode in the non-aqueous
solution exhibits rectangular shape behaviour within the potential range of
1.5V to -1.5V, which is the characteristic of double layer capacitance,
corresponding to the non faradaic reversible reaction of Li ion
adsorption/desorption on the surface of the carbon nano foam.
In the non aqueous solution, it is assumed that oxygen evolution
occurs on the positive electrode when the Li ion is extracted from LiCoO2
(charging process) and hydrogen evolution occurs at the CNF negative
electrode when a Li ion is adsorbed (charge process). The lithium ion can be
completely extracted from layered frame work in the non aqueous solution,
but with electronic conductivity of carbon, the oxygen evolution potential
shifts to a high value of 1.5V. Therefore safe charge potential of layered is
below 1.5V. It is interesting that the lithium ion can reversibly adsorb-desorb
on the CNF in the non aqueous solution containing the lithium ion and
exhibits a good capacitance profile before hydrogen evolution as shown in
the Fig 5.9.
In case of aluminium doped lithium cobaltate, the supercapacitors
with aluminium fraction x=0.2 and 0.6 possess meager specific capacitance
values such as 16 F/g and 8 F/g respectively. But doping aluminium at a
fraction of x=0.4 shows very good results with maximum specific
capacitance value of 27 F/g.
The CV curves after 500 cycles for all the doped and bare LiCoO2
show good reversibility. Base LiCoO2 offers some resistance to degradation
on cycling whereas the cathode materials doped at x=0.2 and 0.6 fail
94
miserably on cycling. But aluminium doping at x=0.4 shows very good
specific capacitance value even after 500 cycles. Thus CV studies prove
LiCo0.6Al0.4O2 as the best candidate for supercapacitor applications. Prof.
Ceder has already proved this for lithium batteries and the same has been
effectively reproduced in this supercapacitor studies.
The specific capacitance of the hybrid supercapacitor cell
(LiCoO2/CNF) from CV is calculated by using the following equation 5.1.
C = i /(v x m) (F/g)……………………………...5.1
Where i = current value calculated from the CV graph(A)

v = scan rate (mV/s)
m = mass of the cathode material (g)
The specific capacitance values calculated from CV for the base and
Al doped materials are tabulated in Table 5.1.
0.0004
0.0002
0.0000
Current(A)
-0.0002
-0.0004
-0.0006
1mV/s
-0.0008 2mV/s
5mV/s
2000 1000 0 -1000 -2000

Voltage(mV)
Fig 5.9: CV of LiCoO2/CNF supercapacitor as fabricated
95
0.0002
0.0000
Current(A)
-0.0002
1mV/s
-0.0004 2mV/s
5mV/s
1500 1000 500 0 -500 -1000 -1500
Voltage(mV)
Fig 5.10: CV of LiCo0.8Al0.2O2/CNF supercapacitor before

cycling
0.0004
0.0002
Current(A)
0.0000
-0.0002
-0.0004 1mV/s
2mV/s
5mV/s
-0.0006
1500 1000 500 0 -500 -1000 -1500
Voltage(mV)
Fig 5.11: CV of LiCo0.6Al0.4O2/CNF supercapacitor as

fabricated
96
0.0002
0.0001
Current(A)
0.0000
-0.0001
1mV/s
2mV/s
5mV/s
-0.0002
1500 1000 500 0 -500 -1000 -1500
Voltage(mV)
Fig 5.12: CV of LiCo0.4Al0.6O2/CNF supercapacitor as

fabricated
0.00015
0.00010
0.00005
Current(A)
0.00000
-0.00005
-0.00010 1mV/s
2mV/s
5mV/s
-0.00015
1500 1000 500 0 -500 -1000 -1500
Voltage(mV)
Fig 5.13: CV of LiCoO2/CNF supercapacitor after 500

Charge/discharge cycles.
97
0.0006
0.0004
0.0002
Current(A)
0.0000
-0.0002
1mV/s
-0.0004 2mV/s
5mV/s
-0.0006
2000 1000 0 -1000 -2000
Voltage(mV)
Fig 5.14: CV of LiCo0.8Al0.2O2/CNF supercapacitor after 500

Charge/discharge cycles.
0.0004
0.0002
Current(A)
0.0000
-0.0002
1mV/s
2mV/s
-0.0004 5mV/s
1500 1000 500 0 -500 -1000 -1500
Voltage(mV)
Fig 5.15: CV of LiCo0.6Al0.4O2/CNF supercapacitor after

500 charge/discharge cycles.
98
0.00010
0.00005
Current(A)
0.00000
-0.00005
1mV/s
2mV/s
-0.00010
1500 1000 500 0 -500 -1000 -1500
Voltage(mV)
Fig 5.16: CV of LiCo0.6Al0.4O2/CNF supercapacitor after

500 charge/discharge cycles.
Table 5.1: Specific capacitance (F/g) values of LiCo(1-x)AlxO2 (x = 0, 0.2,

0.4, 0.6) as calculated from cyclic voltammograms
Specific Capacitance (F/g)

Composition
5mV/s 2mV/s 1mV/s
0 15.93 18.75 20.09
0.2 11.6 15.25 16.3
Before cycles
0.4 21.74 26.93 27.61
0.6 6.1 7.63 8.3
0 4.113 5.29 11.95

0.2 8.274 10.33 12.93
After cycles
0.4 16.225 19.74 21.51
0.6 - 5.1 6.4
99
5.5. Electrochemical impedance spectroscopy
The capacitance of pure LiCoO2 / CNF and doped LiCo1-xAlxO2 (x =

0.2, 0.4 and 0.6)/CNF supercapacitor cells are mainly due to lithium ion
insertion/extraction into/out of the electrode material. The electrochemical
impedance measurement was carried out in the frequency range of 100 Hz to
10 kHz. The spectra in the Nyquist plots (ZI Vs ZII) for supercapacitor cells
having the pure and doped material as cathodes are shown in Fig 5.17 and
Fig 5.18. The plot displays the semicircle and Warburg impedance at low
and high frequencies. The semicircle observed in the high frequency range is
attributed to the resistance offered to Li migration through the bulk of the
electrode (Rs) with the associated capacitance (Cdl). The straight line in the
impedance spectra at low frequency is the impedance related with the
diffusion of the lithium ion (Zw). In the case of aluminium doped LiCoO2
material the straight line is shifted towards horizontal axis except when the
aluminium composition is 0.4.
This suggests that the capacitance of the LiCo0.6Al0.4O2/CNF cell
mainly resulted from the pseudocapacitance caused by the lithium ion
insertion/extraction into/out of the electrode. Table 5.2 shows the impedance
parameter obtained for the supercapacitor cells having the pure and doped
material as cathodes.
The solution resistance of Rs = 4.5Ω was obtained for x = 0.4 and it is
almost constant after 500 cycles. The shifting of the straight line in Nyquist
plot is also minimum for x = 0.4 even after 500 cycles. These results show
that Al substitution is good for electrochemical capacitance when x = 0.4.
100
-80
LiCoO2
LiCo0.8Al0.2O2
LiCo0.6Al0.4O2
-60 LiCo0.4Al0.6O2
ZIm
-40
-20
0
0 20 40 60 80 100
ZRe
Fig 5.17: Electrochemical impedance spectroscopes of

supercapacitors before cycles.
-250
LiCoO2
LiCo0.8Al0.2O2
-200 LiCo0.6Al0.4O2
LiCo0.4Al0.6O2
-150
ZIm
-100
-50
0
0 50 100 150 200 250
ZRe
Fig 5.18: Electrochemical impedance spectroscopes of

supercapacitors after 500 cycles.
101
Table 5.2: Solution resistance(Rs) and double layer capacitance(Cdl) values
of LiCo(1-x)AlxO2 (x = 0, 0.2, 0.4, 0.6) as calculated from
Electrochemical impedance spectrographs.
Properties
Composition Rs Cdl
(Ohm) (mF)
0 3.747 0.6194
Before cycles 0.2 2.392 0.5518
0.4 4.551 0.5491
0.6 5.649 0.6328
0 4.721 0.6567
After cycles 0.2 6.253 0.5778
0.4 4.782 0.621
0.6 6.211 0.711
5.6. Galvanostatic charge-discharge cycle tests
The charge-discharge behavior of the hybrid supercapacitor cell was

examined by chrono-amperometry from 0V to 2.0V at 500µA/cm2 current
density. The E-t response behaved in a mirror fashion during the charge
discharge process which means that a reversible reaction occurs among the
electrode material. During the charging and discharging step curves of
charge/discharge obviously display a sloping variation of the time
dependence of the potential that indicates typical pseudocapacitance
behavior in agreement with the analysis of CV measurement. This behavior
resulted from the electrochemical adsorption/ desorption or redox reaction at
an interface between electrode and electrolyte.
102
The capacitance of the electrode can be calculated from charge-
discharge curves according to the following equation 5.2.
C (F) = Q/∆V = (i x t)/ ∆V…………..…………5.2
The specific capacitance and specific energy of the electrode can be

calculated from the equations 5.3 and 5.4 respectively.
C (F/g) = (i x t)/(∆V x m)………………………5.3
E (kWh/kg) = (i x t x ∆V)/m………...…………5.4
Where i = current of charge/discharge (A)

t = time of discharge (s)
∆V= operating potential (V)
m = amount of active material in one electrode (g)
Table 5.3 shows the specific capacitance, specific energy and specific
power of the bare and doped LiCoO2 at 500 µA Cm2 current density. As can
be seen through the bare LiCoO2 has high specific capacitance it degrades
after some cycles. The maximum specific power of 333 kW/kg was obtained
for x = 0.4 and it is also having the highest specific energy of 12 kWh/kg.
This result indicates that substituted materials especially

LiCo0.6Al0.4O2 for electrochemical capacitor possess excellent cycle life
which probably ascribed to stable Li ion insertion and exertion behavior.
103
2.0
1.6
Voltage(V)
1.2
0.8
0.4
0.0
350 400 450 500 550 600
Time(s)
Fig 5.19: 2nd charge/discharge cycle of LiCoO2/CNF

supercapacitor
2.1
1.4
Voltage(V)
0.7
0.0
5600 5610 5620 5630 5640 5650
Time(s)
Fig 5.20: 500th charge/discharge cycle of LiCoO2/CNF

supercapacitor
104
1.6
Voltage(V)
0.8
0.0
26 28 30 32 34 36 38 40 42
Time(s)
Fig 5.21: 2nd charge/discharge cycle of LiCo0.8Al0.2O2/CNF

supercapacitor
2.0
1.6
Voltage(V)
1.2
0.8
0.4
0.0
1337 1338 1339 1340 1341 1342 1343 1344
Time(s)
Fig 5.22: 500th charge/discharge cycle of LiCo0.8Al0.2O2/CNF

supercapacitor
105
2.0
Voltage(V) 1.6
1.2
0.8
0.4
0.0
600 650 700 750 800 850 900
Time(s)

supercapacitor
2.0
1.6
Voltage(v)
1.2
0.8
0.4
0.0
9120 9140 9160 9180 9200
Time(s)

supercapacitor
106
2.0
1.6
Voltage(V)
1.2
0.8
0.4
0.0
105 110 115 120 125 130 135 140 145
Time(s)

supercapacitor
2.0
1.6
Voltage(V)
1.2
0.8
0.4
0.0
11732 11736 11740 11744 11748 11752
Time(s)

supercapacitor
107
Table 5.3: Various parameters of supercapacitors fabricated using the
synthesized cathode materials as calculated from Galvanostatic
charge-discharge tests
Properties
Composition of Aluminium Specific Specific Specific

capacitance Power Energy
(F/g) (kW/kg) (kWh/kg)
0 11.17 312.5 12.41
0.2 0.415 303.03 0.44
Before cycles
0.4 11.41 333.3 12.68
0.6 1.53 322.58 1.075
0 1.8 312.5 2.01

0.2 0.303 303.03 0.336
After cycles
0.4 3.83 333.33 4.25
0.6 0.88 322.58 0.986
References
1. Yong Gang Wang, J. Electrochemical society 153, 2 (2006) P. A450-
A454.
108
Chapter-6
CONCLUSIONS
109
6. Conclusions
The LiCo1-xAlxO2 (x=0, 0.2, 0.4 and 0.6) cathode materials were
synthesized using soft combustion method from their respective nitrate
precursors using Glycine as fuel. The synthesized cathode materials were
characterized physically by Thermal analysis, XRD and FTIR. From this
physical characterizations we can conclude that the soft combustion method
can be adopted to synthesize LiCo1-xAlxO2 (x=0, 0.2, 0.4 and 0.6) materials.
Hybrid supercapacitors were fabricated using LiCo1-xAlxO2 (x=0, 0.2, 0.4
and 0.6) respectively as cathodes and CNF as anodes. The fabricated
supercapacitors were characterized electrochemically by using cyclic
voltammetry, electrochemical impedance spectroscopy and galvanostatic
charge-discharge cycle tests. Among the four supercapacitor cells the one
which is having the LiCo0.6Al0.4O2 as cathode is having good capacitance
behaviour and retains the first place among the four, letting the
supercapacitor having LiCoO2 as cathode next to it. The other two
aluminium doped compounds didn’t show even a moderate behaviour. From
this we can arrive a conclusion that doping LiCoO2 with aluminium sounds
good for supercapacitor application only if the aluminium fraction is 0.4. We
can also conclude that LiCoO2 itself is a good cathode material for hybrid
supercapacitor since it gives a specific capacitance of 11F/g.
110

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DEVELOPMENT OF NON-AQUEOUS

ASYMMETRIC HYBRID SUPERCAPACITORS

in partial fulfillment for the award of the degree

CENTRAL ELECTROCHEMICAL RESEARCH INSTITUTE

ANNA UNIVERSITY :: CHENNAI 600 025

Certified that this project report titled “DEVELOPMENT OF NON-

Modern power sources concentrate on electric vehicle’s

applications. Supercapacitors are also finding wider applications in

were fabricated using LiCo1-xAlxO2 (x = 0, 0.2, 0.4 and 0.6) as

cathodes respectively and carbon nano foam as anode. The electrolyte

here used was 1M LiClO4 in 50-50 volume mixture of Ethylene

carbonate and Propylene carbonate. Polypropylene is used as

separator. The cathode materials were synthesized using soft

combustion method from their respective nitrate precursors. Glycine

materials were characterized physically by Thermal analysis, XRD

and FTIR. The fabricated supercapacitors were characterized

electrochemically using cyclic voltammetry, impedance spectroscopy

and galvanostatic charge-discharge. The performance of the

supercapacitors was evaluated using the above characterizations. The

specific parameters of the supercapacitors were also calculated.

Among the four supercapacitors the one, which is having the

LiCo0.6Al0.4O2 composition as cathode, is having good capacitance

3. SCOPE AND OBJECTIVE 55

4.4 Electrochemical Characterization Techniques 77

5. RESULTS AND DISCUSSION 87

1.1 Construction of a conventional capacitor 17

EDLC - Electrochemical Double Layer Capacitor

1.1.1 Conventional capacitors

Conventional capacitors consist of two electrodes separated by a thin

Where Q is the electrical charge stored at the electrodes and V the

where ξr (also referred to as k) is the relative dielectric constant of the di-

The above theory can be simply represented by the following schematic

Fig 1.2: Schematic representation of conventional capacitor

A battery is a device that converts chemical energy into electrical

1.1.2.2. Secondary batteries

In secondary batteries, the electrode reactions are reversible and the

1.1.2.3. Emergence of lithium batteries

One of the last century’s most revolutionary battery-related discoveries

1.1.2.4. Cathode materials for Li-ion batteries

LiCoO2 is the most commonly used cathode material in commercial Li-

Supercapacitors are an advanced version of capacitors with unique

Fig 1.3: Formation of double layer during the charging.

Supercapacitor devices consist of two electrodes to allow a potential to

Fig 1.5: Charge/Discharge profile comparison

Rather than operate as a main battery, supercapacitors are more

Device Capacitors EDLC Battery

Charging time µ s–ms m s - minute hours

Specific power > 10,000 1000-3000 <500

1.1.3.1. Advantages of supercapacitors

Low impedance - enhances load handling when put paralleled

1.1.3.2. Limitations of supercapacitors

Linear discharge voltage prevents use of the full energy

1.1.3.3. Electrodes for supercapacitors

The following are used as electrode materials for Supercapacitor.

Carbon-Carbon supercapacitors use the cheapest technology due to the

In metal oxide, pseudocapacitance is developed due to the redox

1.1.3.4. Classification of supercapacitors

Based on the electrode materials listed above the supercapacitors may

Electrochemical double layer capacitors

Fig 1.6: Classification of supercapacitors

Electrochemical double layer capacitors

The term electrochemical double layer capacitor is most commonly

Fig 1.7: Charging at electrode surface

cannot match energy densities of mid level batteries