1

Outlines
 Introduction
History of polymer
Electrolytes
Types of electrolytes
Polymer electrolytes & Clay/Nanocomposites
Types of polymer electrolytes
Review of Literature
Objective Of Research
Material Preparation
Material Characterization
Result and Discussion
Conclusion
References
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Why Polymer
The development of mankind passed through several important epochs, like
Stone Age, Bronze Age, and Iron Age and later on Steel Age (the industrial
revolution).
Past to World War II, the developments in industrial chemistry brought to
the market many synthetic polymeric materials which has close attachment to the
modern civilization, which creates a new era now that we are living in called Polymer
Age.
Polymer Science deals with the polymers, polymer blends, polymer
composites, filled polymers, investigation methods and the study on control of the
properties of these materials.
As the 21st century unfolds, the development in science and technology allowed
researchers to better understand structure-property relationship in polymeric
composite materials. Some important features of nanoscale materials, and the
development in nano science & technology, allow researchers to use them in
polymeric composite materials, which afford unique opportunities to create
novel materials with unique and useful properties. Normally, the term nano
scale is the 1-100 nm range.

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 INTRODUCTION

• Polymer are long chain giant organic molecules assembled

from many small molecules called monomers .
• More monomer molecules joined in units of long polymer.
• Example;
polyethylene

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5
 Properties of Polymers

The physical properties of a polymer, such as its strength

and flexibility depend on:

• Chain length - in general, the longer the chains the stronger

the polymer;
• Side groups - polar side groups give stronger attraction
between polymer chains, making the polymer stronger;
• Branching - straight, unbranched chains can pack together
more closely than highly branched chains, giving polymers
that are more crystalline and therefore stronger;
• Cross-linking - if polymer chains are linked together
extensively by covalent bonds, the polymer is harder and
more difficult to melt.
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Nano structured material

 A nanostructured material is defined as a solid material characterized

by at least one dimension in the nanometre range
In terms of Nano crystalline structure, bulk nanomaterial's can be
composed of a multiple arrangement of Nano size crystals, most
typically in different orientations.
Nanomaterial has two categories: engineered and non engineered
Engineered nanomaterial is specially designed for any specific
purpose, such as CNT, Fullerene, Nano rods etc.
Non-engineered is not specially designed but it occurs in nature.
Such as volcanic ash, fine sand and dust particle and ocean spray.
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 Classification of nanomaterial's
Classification is based on the number of dimensions, which are not confined
to the Nano scale range (<100 nm)
 zero-dimensional (0-D)
 one-dimensional (1-D)
 two-dimensional (2-D)
 three-dimensional (3-D)

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• Three-dimensional space showing the relationships dimensional
space showing the relationships among 0- among 0-D, 1-D, 2-D,
and 3-D nanomaterial's.

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 Method to approach the nanomaterial's

There are two ways of approaching the Nano material.

1. Top down approach
2. Bottom up approach

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What are Nanocomposites?
“ A Nanocomposite is a composite material, in which one of the
components has at least one dimension that is around 10-9 m.
or
“ A Nanocomposite is a multiphase solid material where one of the
phases has one, two or three dimensions of less than 100 nm, or
structure having nano-scale repeat distance between the different
phases that make up the material.

Mechanically the term nanocomposites are differ from conventional

composites due to the exceptionally high surface to volume ratio of the
reinforcing and its exceptionally high aspect ratio.

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Classification of nanocomposites

Polymer based

Nanocomposites
Non polymer
based

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Non-polymer based Nanocomposites

• Metal/Metal nanocomposites
(either in the form of alloy or core-shell structure)
Eg. Pt-Ru
• Metal/Ceramic nanocomposites
(either in the form of nanotube or complicated
nanostructure)
Eg.polysiloxane
• Ceramic/Ceramic nanocomposites
(alloy or ceramic)
Eg. Zirconia- alumina

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Polymer based nanocomposites

• Polymer/Ceramic Nanocomposites
(Layer structure) Eg. Barium-titanate with polymers
• Inorganic/Organic Polymer Nanocomposites
(clusters) Eg. Polymer nanofiber with nanoparticles.
• Inorganic/Organic Hybrid Nanocomposites
(Nanocrystal) Eg. CdS nanocrystals, Poly N- vinyl
carbozole

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 Why polymer nanocomposites are unique

• Increase in electrical break down strength of

polymers.

• Melting temperature, color ,magnetization and

charge capacity is more.

• interacting Zone is increasing such that we can get

our expected property.

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 Electrolytes
electrolyte is any substance containing free ions that make the substance electrically
conducting.
It is mainly used in battery for storing charges. The most typical electrolyte is an ionic
solution.
The basic desired qualities of electrolyte materials are listed below:
 High ionic conductivity at wide range of temperatures: increase the lithium ions during
charging/discharging
 Good thermal stability: The battery operation under appropriate temperature
Wide electrochemical window: prevents side reactions between electrodes and
electrolyte
 Good mechanical property: ease of manufacturing and enhanced safety
 Low cost
 Safety: high flashing point
 Non-toxic: environmental friendly.

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 Types of electrolytes
 LIQUID ELECTROLYTES:
Electrolyte solutions are normally formed when a salt is placed into a
solvent like water and the individual components dissociate due to the
thermodynamic interactions between solvent and solute molecules.
• For example
NaCl(s) → Na+ (aq) + Cl−
When NaCl dissolves in water it dissociates into Na+ and Cl− which form the
liquid electrolyte
 SOLID ELECTROLYTES :
In fast ion conductors are solids in which ions are highly mobile. These materials
are important in the area of solid state Ionics and are also known as solid
electrolytes and super ionic conductors .
Required Properties of the Solid Electrolytes:
High ionic conductivity.(10-1 -10-6 Scm-1
Negligible electronic conduction (<10-6 Scm-1).
Activation energy should be very low

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 Technical Approach of electrochemical devices

• All the electrochemical devices have three main

components
• Anode.
• Cathode.
• Solid Electrolyte.

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 Polymer Electrolytes

Polymer electrolyte may generally be defined as a membrane that

possesses transport properties comparable with that of common
liquid ionic solutions.

Research on polymer electrolytes has been growing since 1973

when Fenton al, developed complexes of alkali metal ions with poly
(ethylene oxide) (PEO) .

 Its technological importance was appreciated in early 1980.

They offer conductivity of the order ranging from 10-8 to 10-4 Scm-1
at temperature between 40 and 100 °C.
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Types of Polymer Electrolytes
Dry solid state polymer electrolytes :
The conventional dry solid polymer electrolytes (SPE) are basically the polymer-salt
complexes prepared by dissolving suitable ion donating salts/acids into high molecular weight
polymers which act as a host.

Gel/plasticized polymer electrolyte:

The second types of polymer electrolyte is called ‘‘gel polymer electrolyte’’ or
‘‘plasticized polymer electrolyte’. The most common organic alkyl carbonate solvents are one
or mixture of the following: propylene carbonate (PC), ethylene carbonate (EC).
Polymer composites electrolytes :
The third types of polymer electrolytes is generally, fillers such as ZrO2, TiO2,Al2O3 and
hydrophobic fumed silica were incorporated in to the polymer matrices and are called
‘‘composite polymer electrolytes’’ or ‘‘composite ceramic electrolytes’’.

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Optimization of polymer salt-clay
Nanocomposites electrolytes

 Highionic conductivity
 Substantial Improvement in
• Voltage stability
• Mechanical stability
• Thermal stability
• Transport properties of cation
 Faster charging / slow discharging.

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Benefits of Clay to polymers nanocomposites
electrolytes
Electrical conductivity
Improvement of mechanical properties,
especially strength
Enhancement of thermal stability
Enhancement of thermal conductivity
Effects at low clay contents because of the
very high aspect ratio

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REVIEW OF LITERATURE
S.N.
Host Polymer Salt Plasticize Clay/Fille Cond. (S cm-1 Characterizations Reference
r r ) Performed
1 -
PAN,CN-PVA, LiClO4, LiPF6 PC,EC 14.6 x10-1 XRD, FTIR Solid State Ionics (2006)
PVDF 22.64x10-3 177, ( 26–32), Pages
2683–2686
Hiromori Tsutsumi et.al.
2 XRD, FTIR
PAN,PVDF ,PEO LiClO4, PC ,EC MMT 8.4 x10-7 46(23Applied Polymer
DMF,LiCF3SO3 7.5x10-6 scienc(2008),2577-
2592
A.L. Sharma et.al.

3
PAN LiCF3SO3 PC,EC MMT 2.39 x10-4 to XRD, TEM Applied Polymer science
3.0x10-7 (2010)118(5),2743-2753
A. L. Sharma et.al.
4
PAN,PEO,PMMA LiCLO4 ,LiASF6 - 4.10×10−3 DSC ElectrochimicaActa,
LiCF3SO3 PC,EC (2000)(45),1361–1369,
Kumudu Perera et.al.
-
5 PMMA LiCLO4,LiAS 0.5x10-3 to NMR Electrochimica Acta
PC,EC (1995)40(8), 991–997
LiN(CF3SO2 1x10-4
G.B. Appetecchi, et.al.

6 - -
PAN LiClO4 , 1x10-5 to DSC Electrochimica
LiCF3SO3 1x10-8 Acta,(2000) 45(2) ,1243–
1247,M Forsyth et.al
7 PMMA LiClO4 MMT 1x10-8 XRD , FTIR Polymer sciences ( 2002
EC
) 43 (19) ,5281–5288 23
Hsien-Wei Chen, et.al.
 Objectives
The following are the objectives of this research work:
 Synthesis of polymer electrolytes by solution cast technique.
 Vibrational Characterization by FTIR technique.
 Studies of high ionic conductivity of polymer electrolyte for
energy storage device .

Materials Under Present Investigation:

In the present study, we emphasis on preparation, characterization
and evaluation of thin polymer nanocomposite based on cross linked
polymer (such as;PEO), salt as lithium hexafluoride phosphate
(LiPF6) and BaTio3 as inorganic filler.
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 Gap Analysis
Since the discovery of the polymers electrolytes in the late 1973s,
many scientists have been working on finding some applications
for the newly discovered of polymers nanocomposite, for such an
energy storage device. But till now, polymer nanocomposite is
used as a liquid or Gel electrolytes but due to presence of solvent
(liquid), these are lot of problem such as leakage, stability in tern
of thermal as well as mechanical properties on the basis of the
exhaustive literature survey .We have reached on a conclusion that
above difficulty can be removed offer the use of solid state
polymer nanocomposite.
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Material Preparation Techniques
• METHODS OF PREPARATION
There are methods of preparation of polymer electrolytes by using:
• Solution Casting Techniques:
Following steps are involved in this method:
(a) Dispersion of ceramic fillers in the salt solution.
(b) Addition of a specified amount of polymer to the mixture.
(c) Mixing by means of stirrer or ultrasonic equipment.
(d) Casting the mixture homogeneously on a substrate.
(e) Finally drying in vacuum or in an inert atmosphere.

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 Flow chart by using the solution-casting
technique
Stage-1

Solvent Stirrling at Polymer

polymer Room
(EC) Sol
Temp

Stage-2
Suitable Ps
Polymer Sol Salt Stirring Complex
(LiPF6)
Stage-3

Casting&Eva-
Ps Complex Clay/Filler Stirring poration

PNC 27
CHARACTERIZATION

• Fourier Transform Infrared Spectroscopy:

 Infrared spectroscopy can be used to identify the chemical composition,
chain structure and physical properties .i.e., chain orientation, crystallinity, and
chain conformation or chain dynamics of the polymer electrolyte sample.

 A common laboratory instrument that uses this technique is a FTIR

spectrometer scanning from 4000 to 400 cm-1 with a resolution of 2 cm-1.

 The vibrational characterization of PEO with different salt ratio was

done by FTIR.

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COND…

• Complex impedance spectroscopy :

 Complex impedance analysis is a powerful technique to characterize the

electrical properties of the electrolytes.
 The complex impedance measurements were carried out using a computer
controlled impedance analyzer in the frequency range of 100 MHz to 1MHz at
an a.c. signal of 100 mV at room temperature.
 The polymer electrolyte film is sandwiched between two stainless steel
block electrodes used as cell for the electrical measurement.
 The complex impedance spectrum data was used to evaluate the bulk d.c.
conductivity and other related electrical properties.
 It is measurement of ionic conductivity of the polymer electrolytes.

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 Result and discussion

FTIR ANALIYIS
A comparison indicates relatively higher fraction of free charge carriers at 15

wt.% clay concentration than 0 wt.%. Beyond this, the free anion These results

clearly suggest convincing evidence for clay assisted ion dissociation effect in

the polymer nanocomposite films. This feasibility due to stronger clay–ion

interaction seems logical in view of the dipolar characteristics of BaTiO3 clay.

The variation in free anion fraction with clay concentration is expected to have

a direct impact on electrical transport.

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Deconvolution pattern of ClO4- in (PEO)14NaClO4+ wt. %BaTiO3
(a)0,(b)15
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 IMPEDANCE ANALYSIS
The fig shows variation of room temperature conductivity as a function of salt
concentration. The dependence of conductivity on salt concentration provides information
on the specific interaction between salt and the polymer matrix. Conductivity of polymer
electrolyte is calculated by the equation σ=T/Rb×A.The highest conductivity is Obtained at
114×10-3 Scm-1 for 15 wt. % of BaTio3. The conductivity is expected to decrease beyond
15 wt. % of BaTiO3 due to decrease in the number of charge carriers which lower the
segmental motion of the polymer chain

Impedance plot at room temperature of (PEO)14NaClO4+ wt.

%BaTiO3(a)0,(b)1,(c)2, (d)5, (e)7, (f)10, (g)15,(h)20). 32
 CONCLUSIONS
PEO-based polymer electrolyte systems with various weight
percent’s of NaClo4 have been synthesized using solution
casting technique. The system with 15 wt. % Batio3 exhibits a
maximum conductivity of 10-3 Scm-1at room temperature. At
the molecular level, FTIR studies provide strong evidence that
there is a specific interaction between PEO, NaClo4 and
BaTio3.

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 REFERENCES
• Fenton, D. E., Parker, J. M., and Wright, P. V. (1973). Complexes of alkali metal ions with poly (ethylene
oxide). Polymer, 14(11), 589.).
• Sadhukhan, S. (2011). Preparation and Characterization of Polymer Electrolytes (Doctoral dissertation).
• Manuel Stephan, A. "Review on gel polymer electrolytes for lithium batteries."European Polymer
Journal 42.1 (2006): 21-42.
• Parajuli, R. R. (2011). Developing conducting polymer nanocomposites with carbon nanomaterials for
molecular detection and fuel cell applications (Doctoral dissertation, Rutgers University-Graduate School-
Newark).
• Giles, J. R. M., Gray, F. M., MacCallum, J. R., and Vincent, C. A. (1987). Synthesis and characterization of
ABA block copolymer-based polymer electrolytes. Polymer, 28(11), 1977-1981.
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sources, 100(1), 93-100.
• Girish Kumar, G., and Munichandraiah, N. (2002). Poly(methyl-methacrylate)—magnesium triflate gel
polymer electrolyte for solid state magnesium battery application. Electrochimica acta, 47(7), 1013-1022.
• Subba Reddy, C. V., Sharma, A. K., and Narasimha Rao, V. V. R. (2006). Electrical and optical properties of a
polyblend electrolyte. Polymer, 47(4), 1318-1323.
• Gao, F. (2004). Clay/polymer composites: the story. Materials Today, 7(11), 50-55.
• Daud, F. N., Ahmad, A., and Haji Badri, K. (2014). An Investigation on the Properties of Palm-Based
Polyurethane Solid Polymer Electrolyte. International Journal of Polymer Science, 2014.
• Patila, S. U., Yawaleb, S. S., and Yawalec, S. P. Conductivity study of PEO-LiClO4 polymer electrolyte doped
with ZnO nanocomposite ceramic filler.

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 A PRESENTATION BY
PARUL KUMAR SHARMA 35
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