CHAPTER - I

INTRODUCTION

1.1. Introduction

1. 2. Classification of Superionic Conductors

1. 2. 1. Single/Polycrystalline

1. 2. 2. Glassy/Amorphous

1. 2. 3. Polymers

1. 2. 4. Composite

1.3. Classification of polymer solid electrolytes

1.3.1. Salt with polymer complexes

1.3.2. Poly electrolytes

1.3.3. Solvent swollen polymers

1.3.4. Formation of polymer-salt complexes

1.4. Scope of the Present Work

1.5. Literature reviews

1.5.1. Rare earth based lithium silicates

1.5.2. Nanocrystalline metal oxides

1.5.3. Polymer solid electrolytes

1.6. Present Work

References

CHAPTER - I

INTRODUCTION

1.1. Introduction

The production, storage and distribution of energy are the main

concern of modern industry and society. Over the past ten years, a

spectacular development has been seen in micro electronics industry but, till

date, the application of integral power sources has not been realized. The

development of new types of electrical power generators and storage systems

are quite essential for further integration of the electronic industry. The self

contained power source is a growing trend in numerous fields such as pocket

calculators, bio-medical devices, cameras and electronic watches [1].

The presently available conventional battery system contains a liquid

electrolyte, generally a concentrated aqueous solution of potassium hydride

or sulphuric acid. This liquid electrolyte has high ionic conductivity and offers

very good contact with electrodes. But the major problems associated with

liquid electrolytes are cell leakage, corrosion, self discharge process, drying

out of the cell, loss of electrolyte and severe restrictions on the capability of

useful discharge at very low temperatures.

Interest in developing thin film solid state batteries was initiated with

the hope that the above problems would be minimized. The solid materials,

which exhibit high ionic conductivity comparable with those of liquid

electrolytes, are known as “Solid electrolytes”. These materials are also

1

referred as “Fast Ion Conductors (FIC)” or “Super Ion conductors (SIC)”,

which are characterized by

a. Ionic bonding

b. High electrical conductivity and

c. Ionic transport number t ion ~1

The history of superionic conductors starts with Faraday’s work on AgI

in 1839 [2]. But the development and the study of the subject started about

four decades back, when the tremendous commercial applications of these

materials were realized. This field has received a further boost with the

advent of the discovery of highly disordered “soft” superionic conductors,

called ion conducting polymers and also called polymer solid electrolytes. A

number of excellent reviews are available [3-6] .

1. 2. Classification of Superionic Conductors

Superionic conducting materials are synthesized in large numbers and these

are classified based on the microstructures and phases.

a) Single / polycrystalline,

b) Glasses / amorphous,

c) Polymers and

d) Composites.

2

1. 2. 1. Single/Polycrystalline

Superionic conducting crystalline materials of different cations (Ag+, Cu+, Li+,

Na+, H+ etc.) and anions (O2-, F-) conductors as charge carrier ions have been widely

investigated & reported [7-10]. Examples of crystalline superionic conducting

materials are listed in table 1.1 along with their conductivity at a particular temperature

[11-39]. Silver ion conductors are mostly based on AgI and are synthesized by

substituting either cations or anions or both. The best reported room temperature

silver ion conductor is RbAg4I5 and it is prepared by RbI + 4AgI on the cation

substitution [11-12] Recent times investigation of cation conductors seemed to

concentrate mainly on large number of lithium based SICs materials because of the

small Li+ ionic radii of with high mobility, high energy density, lightweight and high

electrochemical potential. Some of the distinctly known crystalline Li+ ion conductors

are LiI, Li3N. Li2SO4, Li4SiO4, Li2CO3, Li3AlO4, LiCl-MnCl2 etc.

Table 1.1 Examples of single/polycrystalline superionic conducting materials

Type of SICs Conductivity (Scm-1)

Temp (K) References

Silver Ion Conductors

- AgI 1 420 [13-16]

RbAg4I5 0.27 298 [11-12]

- Ag3SI 2 513 [17] Copper Ion Conductors

- CuI 9 x 10-2 723 [18]

KCu4I5 0.6 553 [18]

- Cu2Se 0.11 423 [19]

Ru4Cu16I7Cl13 0.34 298 [20]

3

Lithium Ion Conductors

Li2SO4 1 1073 [21]

Li4SiO4 1 x 10-3 673 [22]

LiTa3O8 1.5 x 10-2 723 [23]

Li2CdI4 1.0 x 10-1 543 [24] Sodium Ion Conductors

Na - Al2O3 1.4 x 10-2 298 [25]

Na1.62Mg0.71Al10.39O17 2.4 x 10-1 643 [26]

Na1.2Pr0.07Mg0.77Al10.39O17 4.5 x 10-2 643 [26]

Na4.1Al0.1YbZr0.9Si0.1P2.9O12 5.89 x 10-2 673 [27] Potassium Ion Conductors

K2O – Ga2O3 1 x 10-3 573 [28]

K - alumina 6.5 x 10-5 573 [29]

K2O – Fe2O3 1.5 x 10-3 573 [30] Oxygen Ion Conductors

ZrO2 – Y2O3 1.2 x 10-1 1273 [31]

Bi2O3 - WO3 1.0 x 10-1 1023 [32]

Bi2Ni0.1V0.9O5.35 3.05 x 10-4 773 [33]

Bi2Zn0.1V0.9O5.35 1.28 x 10-4 773 [33] Fluorine Ion Conductors

- PbF2 1.5 600 [34]

CaF2 3 x 10-6 600 [35]

LaF3 2 x 10-2 1000 [36] Proton Conductors

HUO2PO4:4H2O 4 x 10-3 298 [37]

Sb2O5:4H2O 3 x 10-4 298 [38]

Polytungsticacid (PWA) 1.7 x 10-1 298 [39]

4

1. 2. 2 Glassy/Amorphous

Superionic conducting glasses have been explored as materials for solid-state

electrical devices because of its thermodynamic properties of high random free

energy for the motion of the carrier ion compared to their respective crystalline

counterpart. In 1973, first, Kunze has reported the high ionic conduction in AgI-

Ag2SeO4 glassy system [40]. Later, the large numbers of high ionic conducting glassy

compounds with different types of ionic species, like Ag+, Cu+, Li+, Na+ , H+ , F- and O2-,

have been reported [41]. The SIC glasses possess not only high ionic conductivity

but also a number of other inherent advantages over their single/polycrystalline

counter parts such as

Wide range of selection of composition,

Chemical durability and thereby obtaining range of property control,

Isotropic properties, high potential,

No grain boundary effect,

Configurational flexibility,

Various forms as tailor made,

Potential electrochemical applications, etc.

Table 1.2 gives some examples of the SIC glassy compounds [41-55]. The Li+

ion conducting glasses find more advantages in the application point of view, since it

possesses high energy density. Hence, Li+ ion conducting glasses are receiving

more attention in scientific as well as technology.

5

Table 1. 2. Examples of superionic conducting glasses

Type of SICs Conductivity (Scm-1)

Temp. (K) Reference

Silver glasses

60 AgI – 30 Ag2O – 10 B2O3 8.5 x 10-3 298 [41]

55 Ag2S – 45 GeS2 1.4 x 10-3 298 [42]

55 Ag2S – 45 P2S5 2.68 x 10-5 298 [42]

66.7 Ag2S - 33.3 As2S3 1 x 10-4 298 [42]

70 AgPO3 - 30 Ag2SO4 5.0 x 10-6 298 [43]

60 AgI – 24 Ag2O – 6PbO – 10B2O3 9 x 10-3 298 [44]

30 Ag2O - 28 B2O3 - 42 TeO2 2.8 x 10-6 373 [45]

Copper glasses

CuI – Cu2O - P2O5 1.0 x 10-2 298 [46]

CuI – Cu2O - MoO3 1.0 x 10-2 298 [47]

CuI – Cu2MoO4 - Cu3PO4 1.0 x 10-2 298 [48]

Sodium Glasses

Na2O - SiO2 2.8 x 10-5 373 [49]

39 Na2O – 8 Y2O3 – 53 SiO2 3.39 x 10-3 573 [50]

60 Na2S – 40 GeS2 1.5 x 10-4 373 [51]

Pottassium Glass

10 K2O – 90 SiO2 1.9 x 10-9 748 [52]

Lead Glasses

40 Pb(PO3)2 – 60 PbCl2 7.08 x 10-6 473 [53]

Fluoride Glasses

Zr – Ba – Cs – F 1.0 x 10-5 473 [54]

Zr – Th – Ba – Li – F 1.0 x 10-4 473 [55]

6

1. 2. 3 Polymers

High ionic conducting polymer solid electrolyte (PSEs) was first reported by

Fenton et al.[56]. Later, Wright et al. studied the cation based polymer solid

electrolytes such as alkali metal salts of LiCF3SO3 & NaSCN, incorporated in poly

(ethyleneoxide) (PEO) & poly (propyleneoxide) (PPO) matrix, in which the Li+ & Na+

are the charge carrier ions.[57]. In 1978, Armond et al proved the potentialities of PSE

as practical electrolyte materials in electrochemical device [58]. The dominant class of

polymer solid electrolytes comprises of the neutral polar polymer complexes with

alkali metals/divalent/transition metal/ammonium salts and acids. The polymer solid

electrolytes consist of ionic salts dissolved in a polymer matrix, and exist as solids but

possess very high ionic conductivity of the order of liquid electrolytes. The most

common complexes of poly(ethyleneoxide) (PEO) and alkali metal salts, MX is as

follows

The alkali salts used in the synthesis composed of anions of mostly

monovalent ions that are large in size, soft and easily polarized derived from strong

Bronsted acid. The most of the lithium salt anions are ClO4-, CF3SO3

-, SCN-, BF4-,

AsF6-, PF6, etc. Table 1.3 gives some examples of polymer solid electrolytes with

conductivity at particular temperature [58, 62-75]. Polymer solid electrolytes are

classified as solvent free polymer salt complexes, solvent swollen polymers and poly-

electrolyte with properties that lie between those of a solid and a high viscous liquid [4,

59-61]. The polymer solid electrolytes have a visco-elasticity and a good thermal

7

stability. Also, it can be easily prepared in the form of thin films. The lithium polymer

electrolyte systems are of practical interest for the development of high energy density

batteries. Lithium, copper, silver, proton and other ionic conducting polymers are

used in the solid-state devices and are available commercially.

Table 1.3. Examples of polymer solid electrolytes

Type of Electrolyte Conductivity (Scm-1)

Temp (K) Reference

Lithium Ion Conductors

(PVdF-PEGDME) – LiPF6 0.93 x 10-4 293 [62]

(PVdF-PEGDME) – LiCF3SO4 1.00 x 10-4 293 [62]

(PEO) - LiCF3SO4 5.5 x 10-4 298 [63]

(PPO)9 - LiCF3SO4 10-6 298 [58]

(PAN/EC/PC) – LiAsF6 2 x 10-3 293 [64]

(PEO/PEG) – LiCF3SO3 1.7 x 10-3 298 [65]

(MEEP/PPO) - (LiClO4) 10-7 298 [66]

(bis-amino PEO/PPO) – (LiClO4) 3 x 10-5 298 [67] Sodium Ion Conductors

(PEO)19 – NaI 10-4 298 [68]

(PPO)12 - NaCF3SO3 10-6 298 [58]

(PEO)4.5 – NaSCN 3 x 10-7 298 [58] (MEEP)4 - NaCF3SO3 10-5 298 [69]

Proton Conducting Polymers

(PVA) - H3PO4 10-5 298 [70]

(PEO) - NH4SCN 10-5 298 [71]

(PEO) - NH4I 10-5 303 [72] Other Polymers

(PEO) – CuI 10-6 303 [73]

(PEO) - KAg4I5 2.0 x 10-3 298 [74]

(PEO)1000 - (NKSO2Me)2 8.5 x 10-6 298 [75]

8

1. 2. 4 Composite

Ionic conductors containing dispersed second phase of electrically insulating

and chemically inert in the parent material to enhance the ionic conductivity are called

composite ionic conductors. The composite electrolytes are in fact multiphase

materials and typically of two-phase solid systems. Liang, in 1973, first observed a

remarkable ionic conductivity enhancement when Al2O3 was added to LiI to form the

LiI-Al2O3 composite.[76] The dispersed second phase particles neither reacted with

nor dissolved in the matrix phase. Table 1.4 gives the list of composite ionic materials

with ion conductivity measured at a particular temperature [76-80]. The composite

ionic materials were further divided into Crystal-Crystal, Crystal-Polymer, Crystal–

Glass and Glass-Polymer composites.

Table 1.4. Examples of composite materials.

Type of Electrolyte Conductivity (Scm-1)

Temp. (K)

Reference

Crystal – Crystal

LiI - Al2O3 1.0 x 10-4 298 [76]

CuCl2 - Al2O3 5.0 x 10-6 298 [77]

AgI-Fly Ash 1.2 x 10-5 298 [78]

AgI - Al2O3 1.0 x 10-3 298 [78]

Li2SO4 - CaSO4 1.0 x 10-3 773 [79]

Li2SO4 - MgSO4 3.6 x 10-3 673 [80]

9

1.3. Classification of polymer solid electrolytes

Polymer solid electrolytes are broadly classified into various categories

a. Salt with polymer complexes

b. Poly electrolytes

c. Solvent swollen polymers

1.3.1. Salt with polymer complexes

These are polymers with salts of monovalent alkali metal/ divalent/

transition/ metals and ammonium salts and these can be prepared easily in

thin film form with better mechanical properties. Hence, these are having

better properties compared to glass or ceramic solid electrolytes. Examples:

PEMA - PVC - PC -.LiClO4

1.3.2. Poly electrolytes

Poly electrolytes are a class of polymers that have self ion-generating

groups, attached with the main chain of the polymers, are responsible for high

ionic conductivity. Some important examples are polysulphonic acid based

poly electrolytes such as Nafion, Sodium, Poly (styrene sulphate), etc. The

main attractions of poly electrolytes are the single ion transport in the bulk.

1.3.3. Solvent swollen polymers

Some solvents (aqueous / non aqueous) make the basic polymer host

like poly vinyl alcohol (PVA) or poly vinyl pyrrolidine (PVP) to swell, which will

allow to dope the ionic solute like H3PO4 in the swollen polymers.[70]

10

1.3.4. Formation of polymer-salt complexes

A polymer such as poly (ethylene oxide) (PEO) and metal salts such as

alkali metal salts are dissolved in suitable solvents. The solvent may be one

component or it may be two-component mixture. The mixed solutions are

casted in the glassy substrate and allowed to evaporate to form thin film.

The most common example concern complexes between poly

(ethylene oxide), PEO and alkali metal salts, MX as

For effective complexation/ salvation of salts in polymers, the following

criterion can be taken as “thumb rules”. The polymers should be of low glass

transition temperatures (Tg) for their flexible backbone, which will ensure the

complexation. The low Tg can be attained either by choosing the polymers of

low cohesive energy (such as PEO, PPO, PEI etc.) or by plasticizing the

polymers of high Tg. The lattice energy of the salts should be lower for which,

salts of larger anions such as I, CIO4-, CIO3

-, CF3SO3, SCN- etc., are most

suitable. The concentration of polar groups (or solvating hetero atoms)

responsible for complexation of cations, should as large as possible. Table

1.3 gives some examples of polymer solid electrolytes with conductivity at

particular temperature [58, 62-75]. Lithium ion based polymer solid electrolyte

systems (polymer (PVdF), polymer blender (PVdF/PMMA) and copolymer

(PVdF –HPF)) are also having higher lithium ion conductivity comparable

with PEO based solid electrolytes.

11

1.4 SCOPE OF THE PRESENT WORK

In general, the rare earth based lithium solid electrolytes have better

structural stability and good ionic conductivity. In order to utilize the

advantages of rare earth based lithium solid electrolytes, in the present

investigation, 1. lithium samarium silicate, 2. lithium lanthanum silicate and 3.

lithium dysprosium silicate were chosen to develop high ionic conducting

inorganic solid electrolytes using sol-gel process. Also, developed three sets

of nanocomposite polymer solid electrolytes using solution casting method

and the required three metal oxides were synthesized using combustion

method. Transport properties of the above compounds indicate that the newly

developed solid electrolytes ( Inorganic & Organic) are found to have high

ionic conductivity and so, these can be used in many ionic device

applications. Hence, the newly developed high ionic conducting solid

electrolytes (Inorganic & Organic) will have so much scope in developing

various types of ionic devices.

1.5 Literature reviews

1.5.1 Rare earth based lithium silicates

Many rare earth based alkali silicates become high ionic conductors,

in which the alkali ions serve as mobile species. Shannon, et al

discussed in detail about Na5YSi4O12, Na1-xZr2Sixp3-xO12, etc are known as

sodium superion conductors (NASICON [81-82], and Goodenough et al

reported the Na 3+3x-yR1-xPySi3-yO9 (R = rare earth), known as sodium rare

earth based phospho silicates (NARPSIO) [83]. Alkali rare earth silicates are

particularly suited for high ion conducting electrolytes because of their open

12

structure. Recently, new class of rare earth based lithium silicates

[LiLnSiO4” (Ln = rare earth ions)] are formulated and reported by

Nakayama et al. [84]. The compounds with Ln = La-Dy are in hexagonal

structure, where as Ln = Ho-Lu and Y are having orthorhombic structure.

The former compounds have much higher ion conductivity than later.

1.5.2 Nanocrystalline metal oxides

Titanium dioxide has been a well-known material because of its wide

range of applications in solar cells, energy storage, environmental

applications, such as photocatalysts for air purification, filters, etc. Because of

the better chemical stability, lower production cost and thin-film transparency,

etc,TiO2 is being given more attention than other materials, such as ZnO,

CdS, ZrTiO4, etc., In recent years, nano sized TiO2 has been synthesized

and used as nano fillers by dispersing in the polymer solid electrolytes to

enhance the electrical conductivity and mechanical properties. Hence, it can

be used as a better electrolyte in various ionic device applications including

lithium ion batteries.

1.5.3 Polymer solid electrolytes

Studies on polymer solid electrolytes have been attracted great

attention due to their potential applications for electric and load leveling

vehicular applications [85-86]. PEO (polyethylene oxide)-based polymer solid

electrolyte is of current interest for high energy density and high power

lithium-ion batteries due to their easy formation of complex with lithium salts,

high mobility of charge carriers, stable chemical properties, etc [86]. In

13

general, polymers are poor ionic conductor and are not suitable for ionic

device applications [85-92]. The ionic conductivity of the polymers can be

improved with the addition of various lithium salts (LiX; X= ClO4,BF4,PF6, etc.)

and liquid plasticizers like ethylene carbonate (EC) or propylene carbonate

(PC) and low molecular weight polyethylene glycol (PEG) to the pure PEO

polymer [93-94].

Further, enhancement of the electrical conductivity and mechanical

properties have been achieved by dispersing nanosized metal oxides in the

above mentioned polymer solid electrolytes for better ionic device applications

including lithium batteries.

1.6. Present Work

The literature survey in the field of high density lithium ion battery

technology inspired to develop the rare earth based lithium silicates as solid

electrolyte. Hence, in the present investigation, lithium samarium silicate

(LiSmSiO4), Lithium lanthanum silicate (LiLaSiO4) and lithium dysprosium

silicate (LiDySiO4) are taken to synthesize by sol-gel process. All the

prepared rare earth based lithium silicate crystalline materials were

characterized by using various techniques such as XRD, FTIR and SEM-

EDX. AC conductivities and electrical modulus were also studied using the

measured impedance data.

Enhanced electrochemical properties of lithium ion based polymer solid

electrolyte have been achieved by dispersing nanocrystalline metal oxides in

them. So, in the present study, nanocrystalline metal oxides TiO2, Dy2O3 and

MgO are synthesized by using combustion process. The crystallite phase

14

and size, absence of the organic residues, the presence of existing elements

were confirmed by XRD, FTIR, TG/DTA and SEM-EDX techniques. The

electrical conductivities are also studied using the measured impedance data

at various temperatures.

The polymer solid electrolytes have attracted an immense interest in

several solid-state devices due to their high ionic conductivity combined with a

tailor made mechanical stability. In the present study, the synthesized

nanocrystalline metal oxides TiO2, Dy2O3 and MgO are dispersed in polymer

systems such as Polymer (PVdF), blended polymer (PVdF/PMMA) and

copolymer (PVdF-HPF). The uniform distribution of nanocrystalline metal

oxides in polymer systems, phase, structure and thermal behavior are

confirmed by XRD, FTIR, DSC and SEM techniques. Electrical conductivities

are also studied using the measured impedance data at various

temperatures.

Low cost, high reliable computerized homemade battery cycle tester is

designed and constructed. The performance of the battery cycle tester is

tested and standardized by using commercially available battery. All the

detailed results and discussions are presented in the respective chapters.

15

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