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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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