FLEXIBLE THIN-FILM BATTERY ON SOLID-POLYMER

ELECTROLYTE

A PROJECT REPORT SUBMITTED IN PARTIAL FULFILLMENT

FOR THE AWARD OF DEGREE
OF

BACHELOR OF TECHNOLOGY
IN

METALLURGICAL AND MATERIALS ENGINEERING

BY
J. JOY SHEFALI N110307

S. CHANDINI N110202

M. SAILAJA N100787

UNDER THE GUIDANCE OF

MR. T. SIVA
Lecturer

DEPARTMENT OF METALLURGICAL AND MATERIALS

ENGINEERING

RAJIV GANDHI UNIVERSITY OF KNOWLEDGE TECHNOLOGIES

RGUKT-NUZVID, ANDHRA PRADESH
(2016-2017)

1
 DEPARTMENT OF METALLURGICAL AND
MATERIALS ENGINEERING
RGUKT NUZVID-521202
Krishna District, Andhra Pradesh.
----------------------------------------------------------------------

CERTIFICATE

This is to certify that the report entitled “FLEXIBLE THIN-FILM BATTERY

ON SOLID POLYMERELECTROLYTE” submitted by
J.JoyShefali(N110307),S.Chandini(N110202) M.Sailaja(N100787) to the
Department of Metallurgical and Material Engineering, Rajiv Gandhi University
of Knowledge Technologies, Nuzvid for the award of the degree of Bachelor of
Technology in Metallurgical and Materials Engineering is a bonafide work carried
out under our supervision and to the best of our knowledge elsewhere has not been
submitted for award of degree

HOD I/C Supervisor

A.VEERA SREENU T. SIVA
Assistant professor Lecturer
RGUKT NUZVID Department of MME

Place: Nuzvid
Date: 08-05-2017

2
 DEPARTMENT OF METALLURGICAL AND
MATERIALS ENGINEERING
RGUKT NUZVID-521202
Krishna District, Andhra Pradesh.
----------------------------------------------------------------------

THESIS APPROVAL CERTIFICATE

This is to certify that the report entitled“FLEXIBLE THIN-FILM BATTERY

ON SOLIDPOLYMER ELECTROLYTE” submitted by J.JoyShefali(N110307)
S,Chandini(N110202),M.Sailaja(N100787) to the department of Metallurgical and
Materials Engineering, Rajiv Gandhi University of Knowledge Technologies,
Nuzvid, Andhra Pradesh is carried out under our supervision

Supervisor

T.Siva
Lecturer
Department of MME,
RGUKT, APIIIT-NUZVID.

Place: Nuzvid,
Date: 08-5-2016.

3
 ACKNOWLEDGEMENT

I wish to express my deep sense of gratitude and sincere thanks to our Head of the
Department Mr. A.VEERA SREENU for his encouragement, timely help and
advice offered to us.

I would like to express our sincere gratitude to our guide Mr.T.SIVA sir, for his
faithful support and encouragement in spite of their busy and tiring schedule and
aiding us in a valuable insight and practical knowledge.

I would also like to take this opportunity to thank Mr. SASTRI Sir lab assistant in
MME department for giving permission and allowing us to undergo our project
work. We would like to extend our sincere thanks to all of them.

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ABSTRACT

Polyvinyl alcohol (PVA) and polyethylene glycol (PEG) are the two
polymers used in our experiment because these are two having better ionic
conductivity , a high lithium ion transference number and excellent interfacial
stability.To enhance the conductivity of polymers three types of electrolytic salts
are added namely magnesium chloride (MgCl2), nickel chloride (NiCl2), Lithium
acetate in different concentrations and combinations. The two polymers are
dissolved separately in double distilled water. Then both are mixed and stirred
continuously for 16 hours to obtain a homogenous polymer blend. The blended
solution is poured into petri dishes and evaporated at room temperature to form a
thin film polymer electrolyte and stored in air tight covers. Stainless steel
electrodes are cut with specific dimensions and polished. X ray diffraction
technique is performed for the polymer films and the diffraction patterns are
plotted and compared.

Key words: Polymer, polyvinyl alcohol, polyethylene glycol ionic conductivity,

X-ray diffraction.

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 TABLE OF CONTENTS

CHAPTER TITLE PAGE NO

1 INTRODUCTION 7-20

1.1 Polymers

1.2 Conducting polymers

1.3 Polymer electrolytes

1.4 Battery

1.5 Principle of a battery

1.6 Capacity and discharge

1.7 C-Rate

1.8 Life time

1.9 Classification of batteries based on type of electrolytes

1.10 Classification of rechargeable batteries

1.11 Magnetic stirrer

1.12 Electrochemical impedance spectroscopy

1.13 X ray diffraction

2 LITERATURE REVIEW 21-22

2.1 Literature review

3 OBJECTIVE AND WORK PLAN 23-24

6
3.1 Objective

3.2 Work plan

4 EXPERIMENTAL DETAILS 25-36

4.1 Materials and Methods

4.2 Experimental procedure

5 RESULTS AND DISCUSSIONS 27-34

5.1 X ray diffraction results

6 CONCLUSIONS 35

7 FUTURE WORK PLAN 36

8 REFERENCES 37

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LIST OF FIGURES

Figure 1. Nickel-Cadmium battery

Figure 2. Nickel-Metal hydride battery

Figure 3. Lead acid batteries

Figure 4. Lithium ion battery

Figure 5. Lithium polymer battery

Figure6. Magnetic stirrer

Figure7. Polymer thin film sample1

Figure8. Polymer thin film sample 2

Figure9. Polymer thin film sample 3

Figure10. Polymer thin film sample 4

Figure11. Polymer thin film sample 5

LIST OF TABLES

Table 1. List of compositions of polymer films

8
 CHAPTER-1

INTRODUCTION

1.1 POLYMERS:

Polymers are substances made up of recurring structural units, each of which

can be regarded as derived from a specific compound called a monomer. The
number of monomeric units usually is large and variable, each sample of a given
polymer being characteristically a mixture of molecules with different molecular
weights. The range of molecular weights is sometimes quite narrow, but is more
often very broad. Their consequently large molecular mass relative to small
molecule compounds produces unique physical properties including toughness,
viscoelasticity, and a tendency to form glasses and semi crystalline structures
rather than crystals

1.2 CONDUCTING POLYMERS:

Polymers have always been considered as insulators of electricity. But, in

1978, first conducting polymer is discovered which is an intrinsically organic
conjugated polymer, exhibits excellent dramatic increase in electrical conductivity
on treatment with oxidizing (electron accepting) or reducing (electron donating)
agents. These oxidation and reduction reactions, which induce high conductivity in
PA are termed as p-doping and n-doping respectively. Conducting polymers
combine the eletrical properties of metals with the advantages of polymers such as
light weight, greater workability, resistance to corrosion and chemical attack, lower
cost and have applications on wide range of products extending from most
common consumer goods to highly specialized applications in space, aeronautics,
electronics and non-linear optics.

9
1.3 POLYMER ELECTROLYTES:

Polymer electrolytes are electrolytic materials that are widely used in

batteries, fuel cells and other applications such as super capacitors, photo
electrochemical and electro chromic devices. Polymer electrolytes have good
interfacial contact with electrode materials. They have adequate conductivity for
practical purposes, low electronic conductivity, good mechanical properties, high
chemical, electrochemical and photochemical stability, ease of processing.

1.4 BATTERY:

A battery is an electrochemical cell which is used to power electrical devices

like lights, smartphones, electric cars etc. It has two terminals namely anode and
cathode which are negative and positive terminals respectively. It also has an
electrolyte which facilitates the movement of the ions generated during the
electrochemical reactions which occur at the electrodes and completes the
electrical circuit.

1.5 PRINCIPLE OF A BATTERY:

Batteries convert chemical energy into electrical energy. A battery may

contain single or some number of voltaic cells. Each cell have two half-cells
connected in series by a conductive electrolyte containing anions and cations. One
half-cell includes electrolyte and anode, to which anions migrate; the other half-
cell includes electrolyte and cathode to which cations migrate. Cations are reduced
(e at the cathode during charging, while anions are oxidized at the anode during
charging. During discharge, the process is reversed. The electrodes do not touch
each other, but are electrically connected by the electrolyte. Some cells use

10
different electrolytes for each half-cell. A separator allows ions to flow between
half-cells, but prevents mixing of the electrolytes

Batteries are broadly classified into two types. They are:

1. PRIMARY BATTERIES:
These are also called as single-use or disposable batteries which can be used
only once and discarded. The electrode materials are irreversibly changed
during discharge. These have higher energy densities than rechargeable
batteries
Eg: Batteries used in torch lights, Zinc-carbon batteries.

2. SECONDARY BATTERIES:
These are also called as rechargeable batteries which can be discharged and
recharged multiple times using mains power from a wall socket. The original
composition of the electrodes can be restored by reverse current.

1.6 CAPACITY AND DISCHARGE:

A battery's capacity is the amount of electric charge it can deliver at the

rated voltage. The fraction of the stored charge that a battery can deliver depends
on multiple factors including battery chemistry, the rate at which the charge is
delivered (current), the required terminal voltage etc. The higher the discharge rate,
the lower the capacity.

Batteries stored for a long period or that are discharged at a small fraction of the
capacity lose capacity due to the presence of generally irreversible side reactions
that consume charge carriers without producing current. This phenomenon is
known as INTERNAL SELF-DISCHARGE. When batteries are recharged,
additional side reactions can occur, reducing capacity for subsequent discharges.

11
After enough recharges, all the capacity is lost and the battery stops producing
power.

Limitations:
Internal energy losses and the ions pass through the electrolyte cause battery
efficiency to vary. Above a minimum threshold, discharging at a low rate delivers
more of the battery's capacity than at a higher rate. High-drain loads such as
digital cameras can reduce total capacity.

1.7 C-RATE:

The C-rate is a measure of the rate at which a battery is being discharged. It is

defined as the discharge current divided by the theoretical current draw under
which the battery would deliver its nominal rated capacity in one hour. A 1C
discharge rate would deliver the battery's rated capacity in 1 hour. A 2C discharge
rate means it will discharge twice as fast (30 minutes).

1.8 LIFE TIME:

For a rechargeable battery, it can mean either the length of time a device can
run on a fully charged battery or the number of charge/discharge cycles possible
before the cells fail to operate satisfactorily. For a non-rechargeable battery, these
two lives are equal since the cells last for only one cycle.

1.9 CLASSIFICATION OF BATTERIES BASED ON THE TYPE OF

ELECTROLYTE:

(i) Wet cell:

A wet cell battery has a liquid electrolyte. These are a precursor to dry cells
and are commonly used as a learning tool for electrochemistry. They can be built
with common laboratory supplies, such as beakers, for demonstrations of how

12
electrochemical cells work. Wet cells may be primary cells (non-rechargeable) or
secondary cells (rechargeable). Wet cells are still used in automobile batteries and
in industry for standby power for switchgear, telecommunication.
Eg: Daniell cell, Leclanche cell, Grove cell, Bunsen cell, Chromic acid cell, Clark
cell, and Weston cell.

(ii) Dry cell:

A dry cell uses a paste electrolyte, with only enough moisture to allow
current to flow. Unlike a wet cell, a dry cell can operate in any orientation without
spilling, as it contains no free liquid, making it suitable for portable equipment.
A standard dry cell comprises a zinc anode, usually in the form of a cylindrical pot,
with a carbon cathode in the form of a central rod. The electrolyte is ammonium
chloride in the form of a paste next to the zinc anode. The remaining space
between the electrolyte and carbon cathode is taken up by a second paste
consisting of ammonium chloride and manganese dioxide, the latter acting as a
depolariser.

(iii)Molten Salt Cell:

Molten salt cell batteries are primary or secondary batteries that use a molten
salt as electrolyte. They operate at high temperatures and must be well insulated to
retain heat.

(iv) Reserve Cell:

A reserve battery can be stored unassembled (unactivated and supplying no
power) for a long period of time. When the battery is needed, then it is assembled
(e.g., by adding electrolyte); once assembled, the battery is charged and ready to
work.

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 Eg: A water-activated battery for oceanographic instruments or military
applications becomes activated on immersion in water.

1.10 CLASSIFICATION OF RECHARGEABLE BATTERIES:

(i) Nickel Cadmium (NiCd) battery

(ii) Nickel-Metal Hydride (NiMH) battery.

(iii) Lead Acid battery.

(iv) Lithium Ion battery.

(v) Lithium Polymer battery.

(i) NICKEL-CADMIUM BATTERIES:

These batteries are invented in 1899. Nickel hydroxide (Ni(OH)2) is used as

cathode, Cadmium (Cd) is used as anode and Potassium hydroxide (KOH) is used
as electrolyte. The cell voltage is 1.2 Volt with double energy density than that of
lead acid batteries. Due to their small size and high rate discharge capacity, they
made portable tools and other consumer applications practical for the first time.
The cells are sealed and utilise a recombinant system to prevent electrolyte loss
and extend the useful life.

Figure 1. Nickel Cadmium batteries 14

ADVANTAGES:

 High charge and discharge rates are possible.

 Flat discharge characteristic (but falls off rapidly at the end of the cycle)
 Tolerates deep discharges - can be deep cycled.
 Wide temperature range (Up to 70°C)

APPLICATIONS:

These are mainly used in motorised equipment, power tools, two way radios,
electric razors, commercial and industrial portable products, medical
instrumentation, emergency lighting, toys etc.

(ii) NICKEL-METAL HYDRIDE BATTERIES:

These batteries are invented in 1986. Nickel-metal-hydride batteries are

similar to nickel-cadmium batteries and the only difference is instead of cadmium,
hydrogen is used as the active element at a hydrogen-absorbing negative electrode
(anode). The anode is made from a metal hydride usually alloys of Lanthanum and
rare earths that serve as a solid source of reduced hydrogen that can be oxidized to
form protons. The cathode is Nickel-hydroxide and electrolyte is Potassium

Figure 2. Nickel Metal Hydride Battery

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hydroxide. The cell voltage is 1.2 Volts. The energy density is more than double
that of Lead acid and 40% higher than that of NiCads. They accept both higher
charge and discharge rates and micro-cycles thus enabling applications which were
previously not practical.
ADVANTAGES:

 High energy density (W/kg), about 50% better than Nicads, but only about
60% of Lithium ion.
 Low internal impedance but not as low as NiCads
 Typical cycle life is 3000 cycles.
 Can be deep cycled. (80% to 100% DOD)

APPLICATIONS:

These are mainly used in low cost consumer applications, electric razors,
toothbrushes, cameras, camcorders, mobile phones, pagers, medical instruments
and equipment, automotive batteries, high power static applications (Telecoms,
UPS and Smart grid).

(iii) LEAD ACID BATTERIES:

Lead acid batteries were invented in 1859. These are composed of a Lead-
dioxide cathode, a sponge metallic Lead anode and a Sulfuric acid solution
electrolyte. The cell voltage is 2 Volts. They are the best choice for automotive SLI
(Starting, Lighting and Ignition) applications because they are robust. During
discharge, the lead dioxide (positive plate) and lead (negative plate) react with the
electrolyte of sulfuric acid to create lead sulfate, water and energy. During
charging, the cycle is reversed: the lead sulfate and water are electro-chemically

16
converted to lead, lead oxide and sulfuric acid by an external electrical charging
source.

Figure 3. Lead acid batteries

ADVANTAGES:

 Low cost.
 Reliable.
 Robust and tolerant to abuse.
 Tolerant to overcharging.

APPLICATIONS
These are mainly used in automotive and traction applications,lighting high current
drain applications

(iv) LITHIUM ION BATTERIES:

These batteries are invented in the year 1973. In a Lithium ion battery, the
anode is Carbon and the cathode is made from Lithium Cobalt Dioxide or Lithium
Manganese Dioxide. As Lithium reacts violently with water, the electrolyte is
composed of non aqueous organic Lithium salts and acts purely as a conducting
medium and does not take part in the chemical action, and since no water is
involved in the chemical action, the evolution of hydrogen and oxygen gases, as in

17
many other batteries, is also eliminated. Lithium ion battery chemistry depends on
an "intercalation" mechanism. This involves the insertion of lithium ions into the
crystalline lattice of the host electrode without changing its crystal structure. These
electrodes have two key properties

1. Open crystal structures which allow the the insertion or extraction of lithium
ions
2. The ability to accept compensating electrons at the same time

Such electrodes are called intercalation hosts.

During discharge Lithium ions are dissociated from the anode and migrate across
the electrolyte and are inserted into the crystal structure of the host compound. At
the same time the compensating electrons travel in the external circuit and are
accepted by the host to balance the reaction. The process is completely reversible.
Thus the Lithium ions pass back and forth between the electrodes during charging
and discharging.

Figure 4. Lithium ion battery

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ADVANTAGES:

 High energy density.

 Rate of self-discharge is much lower than that of other rechargeable cells
such as Ni-Cad and NiMH forms.
 There is no requirement of priming for lithium ion batteries.
 Do not require maintenance to ensure performance.

APPLICATIONS:

These are used mainly in power larger devices like electric cars, portable
devices like mobile phones and digital cameras, Power tools like cordless drills,
Electric vehicles, hybrid vehicles, telecommunications applications.

(v) LITHIUM POLYMER BATTERIES:

The research on lithium-ion cells with gelled polymer electrolytes (GPE)

was started in 1988. Lithium polymer battery is represented as a developing
technology using a polymer electrolyte instead of the more common liquid
electrolyte. This is also called as Solid-state lithium ion battery. The resulting cell
could be thin, flexible and without risk of electrolyte leakage. This technology has
not been fully developed and commercialized and research is ongoing. This
polymer electrolyte is the area of interest of our present work.

Figure 5. Lithium polymer battery

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The simplest approach is to use a polymer matrix, such as polyvinylidene fluoride
(PVDF) or poly(acrylonitrile) (PAN), gelled with conventional salts and solvents,
such as LiPF6 in EC/DMC/DEC. In the strictest sense, gelled membranes are
hybrid polymer electrolyte (HPE) where the liquid phases are contained within the
polymer matrix. Although these polymer electrolytes may be dry to the touch, they
can still contain 30% to 50% liquid solvent.A polymer electrolyte cell can also be
designed by using of inorganic ionic liquids such as 1-butyl-3-methylimidazolium
tetrafluoroborate ([BMIM]BF4) as a plasticizer in a microporous polymer matrix
like poly(vinylidene fluoride-co-hexafluoropropylene)/poly(methyl methacrylate)
(PVDF-HFP/PMMA).

1.11 MAGNETIC STIRRERER

Magnetic stirrers also known as magnetic stir plates. They are very common
in experimental chemistry and biology. They are used to mix components solids
and liquids to get homogeneous liquid mixtures. Common examples include
bacterial growth media and buffer solution. Magnetic stirrers mix solutions using
an external magnetic field that rotates a small magnetic bar that has been placed in
the mixture of interest. Magnetic stirrers minimize the risks of contamination since
only an inert magnet bar which can easily be cleaned, is put inside the sample or
fluid. In addition, using a mathematic stirrer rather than manual stirrers critical for
consistent, reproducible mixing or mixing over long time scales .Protein dialysis
,for example, requires multi-hour or overnight sample mixing and is sensitive to
bacterial contamination. It ca n rotate an internal magnet at variable speeds, mixing
volumes up to one liter. Glassware with a stir bar is placed directly on top of the
stirrer unit. The device is battery-operated and largely isolated from spins by its
plastic case and gasket.

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1.12 ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY:

Electrochemical Impedance Spectroscopy(EIS) is a highly sensitive

characterization technique used to establish the electrical response of chemical
systems in a non destructive manner. EIS characterize the time response of electro
chemical systems using low amplitude alternating current (AC) voltages over a
range of frequencies. Using an electrode setup consisting of a working, reference,
and counter electrodes a known voltage is passed from the working electrode
through an electrolytic solution and into the counter electrode. Quantitative
measurements are produced by the EIS and enable the evaluation of small scale
chemical mechanisms at the electrode interface and within the electrolytic solution.
Therefore, EIS is useful in determining a wide range of dielectric and electrical
properties of components in research fields studying batteries, corrosion, etc.
An electrochemical cell is used to house the chemical reaction and
is electrically connected to the electrochemical spectrometer to obtain the electrical
response of an electrolytic solution. EIS systems are operated using computer
programs specifically designed for EIS testing.
In Electro chemical spectroscopy, three graphs are generated by the software
namely:
1.Nquist plot (z' vs z'')
2.Bode plot (Impedance vs Frequency)
3.Theta vs Impedance plot.
From above graphs we can find impedance of the polymer film from which we
can find conductivity of the polymer film.
For the obtained six polymer films we performed EIS but we didn’t obtain perfect
results by this test.

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1.13 X RAY DIFFRACTION:

The x-ray diffraction analysis is a powerful tool to determine the structure

and crystallization of the polymer matrices. In order to investigate the effect of
blending, XRD analysis has been performed and their respective diffraction
patterns of polymer thin films with different salt concentrations.The dominant
effect that occurs when an incident beam of monochromatic X-rays interacts with a
target material is scattering of those X-rays from atoms within the target material.
In materials with regular structure (i.e. crystalline), the scattered X-rays undergo
constructive and destructive interference. This is the process of diffraction. The
diffraction of X-rays by crystals is described by Bragg’s Law, n(lambda) = 2d
sin(theta). The directions of possible diffractions depend on the size and shape of
the unit cell of the material. The intensities of the diffracted waves depend on the
kind and arrangement of atoms in the crystal structure. However, most materials
are not single crystals, but are composed of many tiny crystallites in all possible
orientations called a polycrystalline aggregate.

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 CHAPTER-2

LITERATURE RIEVIEW

2.1. LITERATURE RIEVIEW:

The research on lithium-ion cells with gelled polymer electrolytes (GPE) was
started in 1988. From then onwards many experiments were done on polymer
electrolyte batteries to improve their efficiency, performance and cost
effectiveness. In these experiments, Lithium and steel are mostly used as anode
and graphite and pyrite (Fe2S) are mostly used as cathodes in different salt systems.
The electrolytes used are of different types namely polymer, polymer blend,
polymer blend strengthened with nano fillers, polymer matrix composites, polymer
gel electrolytes etc.

 Bipolar Li/composite polymer electrolyte(CPE)/pyrite(Fe2S) battery. The

electrolyte used is LiI1 P(EO) 20 EC1 9% v/v Al2O3 which is 100- 150 m
thick. The salts used in the electrolyte are LiN(CF3SO2)2 and LiCF3SO3.[1]
 Li anode, P(EO) 20-EC1 (9% by volume) Al2O3 CPE electrolyte, 50% v/v
pyrite based composite cathode. The operating temperature is 135 0C.[2]
 Polymer blended films of polyethylene oxide(PEO) (45wt%) and poly vinyl
pyrrolidone(PVP) (45wt%) as electrolyte and Li perchlorate(LiClO4)
(10wt%) as salt embedded with Ag nano filler(4wt%).This is suitable for
solid state battery applications.[3]
 Li/CPE/pyrite battery. Different electrolytes are used namely –Mixture of
propylene carbonate(PC) and Dimethoxyethane and LiCF3SO3 salt dissolved
in it, P(EO)20, Hybrid polymer electrolyte with LiClO4.[4]

23
 Polymer blends of poly vinyl alcohol(PVA) and poly acrylic acid(PAA) are
prepared. Ionic liquid 1- butyl-1-methyl pyrolidinum bis(tri fluro methane
sulfonyl) amide was added to get hybrid polymer.[5]
 Polyethylene glycol(PEG) borate ester (PE-350B) and PEG-
methacrylate(PME-400 and PDE-600) plasticized by borate ester.[6]
 Non aqueous Li-air battery with gel polymer electrolyte (GPE). GPE:
Polypropylene-supported poly methyl methacrylate-blend-polystyrene with
doping nano fumed SiO2.[7]
 PEO based solid polymer electrolyte films with KHCO3 and KHCO3+
plasticizer (Dimethyl formamide-DMS). It is a K+ ion conducting
electrolyte.[8]
 Polymer electrolyte membranes based on: PEO and Ionic liquid- 1-butyl-3-
methylimidazolium methyl sulphate and the salt used is sodium methyl
sulphate.[9]
 A composite separator for lithium –sulphur battery. Lithium ion exchange
membrane is a single ion conductor serving as an electrolyte in batteries.
Sulphur is used as cathode.[10]
 Lithium sulphur (Li-S) battery. Lithium polysulfides in liquid electrolyte
(LE) is replaced with a gel polymer electrolyte(GPE),a facile in-sity
synthesis of pentaerythrito tetraacrylate(PETEA)- based GPE,sulphur
cathode and Li –S battery with a low electrode/GPE .[11]
 Lithium ion conducting biodegradable gel polymer electrolyte based on a
poly(e-caprolactone) : lithium tetrafluoraborate(PCL:LiBF4) system doped
with 1-Ethyl-2-methyllimidazolium tetrafluoroborate(EMIMBF4),
composition of 85PCL:15LiBF4+40EMIMBF4.[12]

24
 A new-fangled nonaflate anion based ionic liquid terynary gel polymer
Electrolyte mixture such as lithium nonafluorobutanesulfonate(LiNfO) and
1-butyl-3-methylimidazolium nonafluorobuatanesulfonate (BMImNfO) in
pol vinylidenfluoride-co- hexafluoropropylene PVdF –co-HFP) matrix.[13]

25
 CHAPTER 3

OBJECTIVE AND WORK PLAN

OBJECTIVE:

The objective of the work is to prepare polymer blend with different electrolytic
salt concentration and form a thin film electrolyte from it. To perform the xrd
analysis for the films and plot the diffraction patterns from the data.

26
 WORK PLAN:
Poly Vinyl Alcohol-PVA Poly Ethylene Glycol-PEG

Dissolve PVA in double Dissolve PVA in double

distilled water to form a distilled water to form a
solution. solution

Add electrolytic salts and blend

the PVA and PVG to obtain a
homogenous solution

Evaporate the blend to form a

thin polymer film

Perform Electro chemical Impedance Perform X-ray Diffraction

Spectroscopy for the films technique for the films

To plot the graphs from

CHAPTER 4 the data
and obtain the results

27
 CHAPTER 4

EXPERIMENTAL DETAILS

4.1 MATERIALS AND METHODS:

ELECTROLYTE: Polymer blend of Poly vinyl alcohol (PVA) and Poly ethylene
glycol (PEG). Both the PVA and PEG are water soluble polymers possessing
superior electrochemical performance with high ionic conductivity, a high lithium
ion transference number and excellent interfacial stability.

ANODE: Mild steel.

CATHODE: Mild steel.

ELECTROLYTIC SALTS: Magnesium chloride (MgCl2) and Lithium acetate

(C2H3LiO2) and Nickel chloride (NiCl2) are the three different types of salts used
to increase the ionic conductivity of the polymer electrolyte. These salts are added
in different proportions and concentrations to the polymer electrolyte and tested.

List of compositions of polymer films:

S.No PVA PEG C2H3LiO2 MgCl2 NiCl2

1. 4.5gms 4.5gms 0.5gms 0.5gms -
2. 4.5gms 4.5gms 1gm - -
3. 4.5gms 4.5gms - 1gm -
4. 4.5gms 4.5gms 0.5gms - 0.5gms
5. 4.5gms 4.5gms - - 1gm

Table 1: The above table shows compositions of five different polymer thin films

28
4.2 EXPERIMENTAL PROCEDURE:
Experimental procedure involves the first step is formation of a polymer thin film.

FORMATION OF POLYMER BLEND:

In this experiment to form a thin polymer film, we have taken two polymers
namely poly vinyl alcohol, poly ethylene glycol, double distilled water and salts of
Magnesium chloride (MgCl2) and Lithium acetate (C2H3LiO2) and Nickel chloride
(Nicl2). Initially take two polymers with respective weights in double distilled
water in a 500ml beakers separately. To dissolve poly vinyl alcohol, 600C
temperature is applied for about 2 hours by using magnetic stirrer. After complete
dissolution, the polymers were mixed with salts in a single beaker using magnetic
stirrer. To form homogenous solution, the stirring continued for about 16 hours.
The solution was poured on to petri dishes and evaporated slowly at room
temperature. After drying the films were peeled off from petri dishes and stored.
We have formed five different polymer thin films with different salt concentrations
and combinations. We have followed the same procedure for every film.

29
 CHAPTER 5

RESULTS AND DISCUSSIONS

5.1 Polymer Thin films:

The five polymer films formed in petri dishes are peeled and stored in air tight
covers to avoid contamination. The pictures of the films are shown below.

Fig7:Polymer thin film Sample 1 Fig8:Polymer thin film Sample2

30
Fig9:Polymer thin film Sample 3 Fig10:Polymer thin film Sample4

Fig11:Polymer thin film Sample5

31
5.1 X RAY DIFFRACTION RESULTS:

Graph 1: The above graph gives the XRD pattern for the polymer blend with Lithium (C2H3LiO2)

Graph 1 shows the XRD pattern of polymer blend with Lithium (C2H3LiO2) This
sample produces diffraction pattern with large number of peaks. XRD analysis has
been performed and their respective diffraction patterns of pure and complex
system are compared. Major peaks that are observed from above graph angle at 20

32
degrees and 24 degrees which equal to 2 theta values. Results are obtained and
compared.

Graph 2: The above graph gives the XRD pattern for the polymer blend with Lithium
C2H3LiO2 magnesium chloride(Mgcl2)

Graph 2 shows the XRD pattern of polymer blend with Lithium (C2H3LiO2) and
magnesium chloride(Mgcl2) This sample produces diffraction pattern with large
number of peaks. XRD analysis has been performed and their respective
diffraction patterns of pure and complex system are compared. Major peaks that

33
are observed from above graph angle at 20 degrees and 22 degrees which is equal
to 2 theta values. Results are obtained and compared.

Graph 3: The above graph gives the XRD pattern for the polymer blend with Lithium C 2H3LiO2 Nickel
chloride(Nicl2)

Graph 3 shows the XRD pattern of polymer blend with Lithium (C2H3LiO2) and
Nickel chloride(Nicl2) This sample produces diffraction pattern with large number
of peaks. XRD analysis has been performed and their respective diffraction
patterns of pure and complex system are compared. Major peaks that are observed

34
 from above graph angle at 19 degrees which is equal to 2 theta values. Results are
obtained and compared.

Graph 4: The above graph gives the XRD pattern for the polymer blend with magnesium
chloride(Mgcl2)

Graph 4 shows the XRD pattern of polymer blend with magnesium

chloride(Mgcl2) This sample produces diffraction pattern with large number of
peaks. XRD analysis has been performed and their respective diffraction patterns
of pure and complex system are compared. Major peaks that are observed from
above graph angle at 20 degrees and at 24 degrees which is equal o2 theta. Results
are obtained and compared.

35
Graph 5: The above graph gives the XRD pattern for the polymer blend with Nickel chloride (Nicl2)

Graph 5 shows the XRD pattern of polymer blend with Nickel chloride (Nicl2)
This sample produces diffraction pattern with large number of peaks. XRD
analysis has been performed and their respective diffraction patterns of pure and
complex system are compared. Major peaks that are observed from above graph
angle at 19 degrees which is equal to 2 theta. Results are obtained and compared.

36
 CHAPTER 6

CONCLUSIONS

 The polymer blends are prepared for five different concentrations and
combinations of electrolytic salts.
 Polymer thin films are successfully prepared from liquid blend.
 Electrochemical Impedance Spectroscopy is performed for the films by
using mild steel electrodes. EIS studies form mild steel failed to explain the
conductivity of thin films.
 X ray diffraction analysis explained the formation of polymer blends.

37
 CHAPTER 7
FUTURE WORK PLAN

 EIS studies of prepared thin films will be studied using stainless steel
electrodes.
 Polymer blends can be prepared with different composition of polmers.t
values.

38
 CHAPTER 8

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[13]-K.Karuppasamy,P. Anil Reddy a, G.Srinivas a,Amit Tewari*2016-
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