1.1. General introduction
1.2. Ionic solids
1.2. 1. Point defect type
1.2.2. Molten sub lattice
1.3. Classification of ion conducting solids
1.3. 1. Normal ionic conductors (NICs)
1 . 3 . 2 Superionic conductors (SICS)
1.3.3 Difference between NlCs and SlCs
1.4. Characteristics of superionic solids
1.5. Classification of superionic conductors
1.5. 1. Superionic conductors based on the mobile species
1. 5. 1. 1. Anionic conductors
1.5.1.2. Cationic conductors
1.5.2. Superionic conductors based on phase and microstructure
1.6. Review on silver ion conducting glasses
1.7. Models for ion transport in glasses
1.7. 1. Anderson and Stuart model
1.7.2. Random site model
1.7.3. Weak electrolyte model
1. 7.4. Diffusion path model
1.7.5. Diffusion controlled relaxation model
1.8. Applications of superionic conductors
I . 9. Present Research Work
References
1 . 1 . General Introduction
Solid state ionics (SSI), an interdisciplinary area of research for the physicists,
chemists, material scientists, engineers and technologists, deal with the properties of ionic
solids, which exhibit a wide range of ionic conductivity (10.' to 10.'' ~ c m " )at ambient
temperature [l-81. Some class of ionic solids exhibit higher conductivity order of
I
10"' Scm'
or more are called superionic conductors (SICs) or fast ionic conductors (FICs) or solid
electrolytes (SEs), since the value of conductivity is the order of liquid electrolytes with
negligible electronic conductivity [O-211.
Superionic conductors (SICs) have bccn attracted considerably due to their
potential applications in various clectrochemical devices, such as, solid state batteries,
sensors, timers, fuel cells, memories, capacitors, etc. Most of the conventional ionic
devices were made up of liquid electrolytes and these have many limitations like (i) short
self life time period, (ii) corrosion reactions occurring between the electrolyte solutions
and electrodes, (iii) leakage, (iv) Instability towards the temperature variations, (v)
miniaturization not possible, etc. These limitations have initiated the interest to search for
new solids with high ionic conductivity [I-71. Hence, many scientists and technologists
have been involved in developing not only SIC materials but also, simultaneously,
involved in developing the solid state ionic devices. The main attractive properties of
superionic conducting materials are high ionic conductivity, stability, ruggedness,
miniaturization, wide range of operating temperature, etc [4, 51. Many superionic
conducting materials are synthesized by various techniques such as melt quench, sol-gel
process, solid state reactions, thermal evaporation, sputtering, etc., for different ionic
device applications. Based on the microstructures, SIC materials are classified as
singlelpolycrystalline, amorphouslglassy, composites and polymers. SIC materials are also
classified based on their ionic species, such as, A ~ ' , cut, ~ i ' ,~ a ' ,F-, 0'- etc, which are
found to exhibit high ionic conductivity (10-141. The amorphouslglassy compounds are
found to have the following advantages compared to their singlelpolycrystalline
counterparts, i.e. (I) Ease in preparation, (2) High ionic conductivity, (3) Absence of grain
boundaries, (4) Isotropic properties, ( 5 ) Inert to atmosphere, etc. Various types like binary.
pseudo-binary, ternary, etc., in different forms like bulk. powders, thin films, etc., of
superionic conducting glasses were prepared and the followiny is the general expression
for ternary SIC glassy systems [I-191.
MX + M20 + F,,O,
(1)
(M = Ag, Li, Na, etc., X = CI, Br, 1, etc., F,O,= P205, SiOz, B203, etc)
Where, MX is the dopant salts (D), M2O are the glass network modifies (m) and
F,,O, are the glass formers (f). Recently, it was found that the addition of one more glass
former increases the glass forming region as well as the conductivity when compared to the
ternary systems. These SIC are called quaternary (four component) superionic conducting
glassy materials with the following general formula.
MX + M2O + (FI, 0, + F2, O,,)
(2)
Where, FI, 0, + F2; 0,. are the two glass forming oxides.
Compared to the other class of SIC compounds, silver ion conductors, especially
glassylamorphous phase, are found to exhibit high ionic conductivity, stability, etc, and
are also found to be promising materials for many solid state ionic device applications [I 7,20-221. Also, glasses with metal oxides, such as Te02, as a network former, are found to
be very atfractive both from the academic and the technological points of view. Tellurium
oxide based glasses are considered to be an important material in the field of glass
technology, particularly, because of their electrical and optical properties [22-351.Tellurite
glasses possess better glass forming ability, high thermal expansion coefficients, low glass
transition temperature (T,) and low melting point [36-381. Silver based tellurite glasses
showed wide range of conductivity order that varies from 1 0 'to
~ 10.' ~ c m - 'Silver
.
based
quaternary tellurite glassy systems with two glass formers showed better conductivity than
three components [39-501. Silver based teltunte glasses are not only having the above
mentioned solid state ionic device applications but also have many optical device
applications like optical switches, fibers, wave guides, etc. 151-541.
The above advantages focused our attention to prepare new quaternary silver based
tellurite glassy systems. Hence, the present investigation is aimed at preparation,
charactcnzation, transport studies and solid state battery applications of three different sets
of new silver based quaternary tellurite SIC glassy compounds. The tetravalent (Te02)and
pentavalent (V205, PzOr,As205)oxides are selected as two network glass formers.
1.2. Ionic Solids
In crystalline solids, ionic conduction occurs because of imperfections or defects
and also due to the long-range diffusion of ions. This effect was first observed by Faraday
in 1839 in many materials, including PbF2. Later, it was shown by Tubant and Lorenz in
1913 [55]. The flow of ions through the lattice occurs in two ways, i.e. via interstitial sites
(Frenkel disorder) or hopping through the vacancies at the normal lattice sites (Schottky
disorder). The defects (or) disorders ionic solids are classified into two types as follows
1. Point defect.
2. Molten sub-lattice.
1.2. 1. Point defect
A Point Defect involves missing of a single atom in the normal crystal array. There
are three types of point defects: Vacancies. Interstitial and Impurities. They may be built-in
with the original crystal growth. Point defect type of solids is further subdivided into two,
according to the defect concentration.
(a). Diluted. n 510" cm-', Ex. NaCI, KCI, AgCI,
P AgI
etc.
(b). Concentrated. n=10~"cm.', Ex. Zr02,CaF2, etc
1 . 2 . 2 . Molten sub lattice
In molten sub lattice type solids, all ions are available for conductions, since the
number of defects or void sites in the sub-lattice are more than the number of ions. So, ions
can move freely from one position to another with low activation energy possessing high
conductivity is called superionic conductors (SICS).
Rice and Roth classified the ionic solids into three types (i). Conventional ionic
solids, in which the defect concentration is low. The numbers of mobile defects are
- 10"
cm-' or less. These are same as "dilute type point dcfect". (ii) These are same as
concentrated type point defect. The defect concentration is
- 1 0 ~cm-'
" . (iii). These are the
"molten sub-lattice type", in which all the ions in a sub-lattice are available for movement.
The numbers of mobile ionic charge carriers are
- 1 oZ2cm-'.
In order to increase the conductivity of an ionic solid, we need to:
1). Raise the temperature and so increase the number of intrinsic defects; or
2). Add an impurity to create vacancies or defects in the structure (extrinsic
defects); or
3). Lower the activation energy of the jump, perhaps by creating more space in the
structure.
1.3. Classification of ion conducting solids
According to the order of conductivity, ionic solids can be classified into two major
categories as follows,
(a) Normal ionic conductors (NICs)
(h) Superionic conductors (SICs)
1 . 3 . 1 . Normal ionic conductors (NICs)
Ionic conductors having the conductivity order of
to 10.' ~ c m -at' ambient
temperature are called normal ionic conductors (NICs). Examples, KC], NaCI, etc. The
activation process involves both energy, due to defect formation (HI) as well as energy due
to ion mib~ation (h,,) [ 5 5 , 561. The conductiv~ty expression for the normal ionic
conductors,
cr =aorl'exp (-Hr)12KT)exp (-h,,lZKT)
(3)
where, a is conductivity,
k
factor)
oo=e2uof h 2 ~ x / (pre-exponential
T is absolute temperature
Hf is ion defect formation
h, is ion migration
K is Boltzman constant
e is charge
uo is jump frequency
1.3. 2 Superionic conductors (SICs)
Some ionic solids have a high conductivity of the order of 10.' ~ c m -or
' more with
negligible electronic conductivity of the ordm of 10'12 ~ c m -at' room temperature as well
as high temperature [I-51 are called 'superion' conductors (SICs), the conductivity
expression for SICs is
0 =oe/T exp (-h,,/2KT)
(4)
Fig. 1. 1. shows the Log o T vs. lOOOK plots of some NICs, crystalline and glassy SICs
1.3.3. Difference between NlCs and SICs:
Normal ionic conductors (NICs)
1. Conductivity is low ( 1 0 . ' ~- 10.'
Superionic conductors (SICS)
1 . Conductivity is high (10"
~cm-')
-
10"
~cm~')
2. May have appreciable electronic 2. Negligible electronic conductivity.
conductivity.
3. Number of mobile charge carriers
are
strongly
3. Mobile charge carriers are almost
temperature
temperature independent (10~*crn")
dependent.(10'6-10'X cm-')
4. Activation energy is high.
4. Activation enerby is low.
5. High conductivity just below the 5.
melting point.
High conductivity well below the
melting point.
1.4. Characteristics of superionic solids
Superionic solids have the following charactcristics,
(i). Crystal bonding is ionic.
(ii). Electrical conductivity is high. (10" Scm" and above)
(iii). Principal charge carriers are ions. It means that the ionic transference number (ti)
is almost equal to 1.
t, refers to the fractional contribution of the ionic
conductivity to the total conductivity.
(iv). The electronic conductivity is negligibly small.
Fig.1.1. Log OTvs. 1000/T plots of crystalline NiCs and SICS
1.5. Classification of Superionic Conductors
All the superionic conductors can be classified based on the mobile ions and also
based on the microstructure/ phase of the solids.
1.5.1. Superionic conductors based on the mobile species
In superionic conductors, either cations or anions can move. So, based on the
mobile ions, these are classified into two different types.
1. Anionic conductors
2. Cationic conductors
1.5. 1. 1. Anionic conductors
Superionic conductors with negative ions as charge carrlers are called anionic
conductors. Anionic conductors do not exhibit good ionic conductivity at ambient
temperature. There are two types. (a) Oxide ion conductors and (b) Fluoride ion
conductors.
(a). Oxide ion conductors
Motion of oxygen ion is responsible for the conduction mechanism. Most of the
oxygen ion conductors show significant value of conductivity only at high temperatures
(1273 K). Also, their conductivity depends strongly on the doping of aliovalent impurities
(Ca 2', Y
'+,Sr 2t, etc. in Hf02, Ge02 etc), which control the number of point defects and
their mobility.
etc.
Examples: Bi2Zno,Vo9 0 5 35, Bi203-WO3, ZTOZ-YZO~,
(b). Fluoride ion conductors
In general, fluoride ion is more conductive than oxide ion, because, the former is
univalent even though the ionic radii of these two ions are almost the same.
Example: CaF2, SrF2, KBiF4, LaF,, Zr-Ba-CCs-F etc [57,58].
1.5. 1.2. Cationic conductors
In these, electrical conductivity is due to the presence of positive ions as charge
caniers are called as cationic conductors. Examples are ~ i ' ~, a ' ,Ca', ~ g ' etc
, [59,60].
(a). Lithium ion conductors
Lithium ion is the mobile canier in thc lithium superionic conducting (LISICON)
compounds. The ionic radius of lithium ion is small compared to those of K' and Rh' ions.
Hence, lithium compounds are hav~ngmore conductivity than Na' & K' ion conductors.
Lithium compounds are useful for high energy density batteries due to their high
electrochemical potential [61-661. Some of the lithium ion conductors are Lil, U3N.
LiAISi04, LisGaOd, Li4A104,LihZn04,and Li'
- ~ a P' alumina.
(b). Copper ion conductors
In these, the monovalent copper ions are the charge caniers and are responsible for
the high ionic conductivity. Examples are aCul, CuzCd4, Cu2Hg14,Cu2Se, Rb4C~lh17C113
and KCu415 [67].
(c). Beta alumina conductors
One of the most extensively studied classes of superionic conductors is the goup of
materials having the general formula n A203B20.(A " = A1
'+,Ca It, Fe '*, B = Nat, K',
Rb', A ~ +TI',
, H,o+, etc.). In these compounds, the conductivity is due to the motion of B'
ions in the loosely packed structural planes of the crystal lattices. Such materials have been
used mostly in the development of high energy density batteries. The 0 alumina superionic
conductors are suitable for high temperature applications [68]. A typical example is
sodium sulfur battery.
(d). Protonic conductors
Proton conducting solids are useful for the fuel cells, sensors, electrochromic
devices, etc. Hydrogen uranyl phosphate HnUOz (10h)2.4 H20 has been effectively
employed as solid electrolytes in fuel cells. Other examples are polyamides and
polysulfinimide, etc [69-721.
(e). Silver ion conductors
In these compounds, silver ions are the mobile carriers. These solids showed high
ionic conductivity at ambient temperature compared to all other types. Some examples arc:
Ag64W04, RbAy4l5, KAgJ.5, NH4Ag4Is,Ag714PO4, Agb14CrO4. Ag,,I4Mo04, etc. [73. 741.
1.5.2. Superionic conductors are also classified based on phase & microstructurc
(a). Crystalline I Polycrystalline
(b). Amorphous 1 Glass
(c). Composites
(d). Polymers
(a). Single I polycrystalline
Number of crystalline cation ( A ~ ' CU',
,
~ i ' .~ a ' H+,
, etc), anion (02-,F-' and mixed
ion ( K', ~ b ' , ~ g ' ,I-, CN-, p alumina, etc) SIC compounds have been reported. The silver
ion conducting compounds are mostly based on Agl and are synthesized by substituting
either cation or anion or both. Examples of crystalline superionic materials and their
conductivity are listed in Table-l . 1 [ 1-7.57-741.
Table 1.1. Examples of crystalline superionic materials
Material
Silver ion conductors
a-Ag,S1
RbAg41s
a-Agl
Lithium ion conductors
Li2SO4
LidSi04
LiTa3O8
Copper ion conductors
a-Cul
KCuds
Potasium ion conductors
K P-Alumina
Oxygen ion conductors
I
Temp. (K)
I
Conductivity ( ~ c m - ' )
za2ty203
Bi203+W03
Fluorine ion conductors
R-PbF2
CaF2
Proton ion conductors
SbzO~:4H20
Polytungsticacid
(b). Amorphous I Glass
Glassy superionic solids are found to exhibit an excellent conductivity due to thcir
structural and thermodynamic properties. A wide range of glass formers have been used to
form different types of local structures. The conductivity increases generally with the
addition of alkali oxides and halides. Presence of two glass formers may also enhance the
conductivity. Large number of high ionic conducting glassy compounds with different
types of ionic species, like ~
gcut,
~ ~ ,i ' ,~ a ' , H', F~,and 02have been reported. Fig.l.2.
shows Log oT vs. lOOOiT plots of some of the SIC glassy systems. The glassy materials
have many other advantages over their single i polycrystalline counter parts and these are,
(i).
Isotropic properties
(ii).
Ease in preparation of thin films
Fig. 1.2. Log OTvs. 1000/T plots of SIC glassy systems
(iii).
Wide selection of glass forming systems
(iv).
Absence of grain boundaries
(v).
Ease of shaping into various forms
(vi).
Inert to atmosphere
(vii). Wide range of control of properties with change in composition
(c). Polymer Solid Electrolytes IPSEl
Many high ion-conducting polymers, which are known as polymer solid
electrolytes (PSE), have been reported. PSEs are synthesized by dissolving the salt of
alkali metals of type MX (M=Na, Li, Ag, NHI, Cu, etc) and (X= I, CI, F, etc) in polymers
like polyethylene oxide. polypropylene ox~de,etc. Polymer solid electrolytes arc classified
as solvent free salt complexes, solvent swollen polymers and polyelectrolytes. These can
be prepared in the fonn of bulk as well as thin films [70-801. Table I . 2 show some
examples for polymer solid electrolytes and their conductivity.
Table 1. 2. Some examples for polymer solid electrolytes and their conductivity.
(d). Composites
Composites are also called dispersed or multiphase heterogeneous solid
electrolytes. C.C. Liang has reported the enhancement in the ionic conductivity of lithium
ion in the Lil- ,41203 system [81]. Composites are classified into four categories.
(i). Crystal-crystal
(ii). Crystal-polymer
(iii). Crystal-glass
(iv). Glass-polymer
Designing composite solid electrolyte with better control of important physical and
chemical properties is an active area of research.
1.6. Review on Silver Ion Conducting Classes
Numerous binary and ternary ~ g conducting
'
glasses arc synthesized and reported.
Minami et al. investigated several ternary Agl - A a 0 - MxOy (Moo3, P205 etc.,) systems
and reported, their glass forming regions and ionic conductivity [82]. Fig 1.3 (a) shows the
structure of bcc unit cell of high conducting a
- Agl, in which the
two silver ions are
statistically distributed over 42 sites of 6 octahedral, 12 tetrahedral and 24 trigonal
bipyramidal. Fig 1.3 (b) shows silver ion occupancy sites in a - Agl. In 1998 & 2001, M.
Tatsumisago, et al, investigated the Agl - ADO - B203superionic conducting glasses by
incorporations large amount of sliver iodide in to the glassy matrix [83]. Malugani, et al.
investigated glass formation in the systems AgX
-
AgP03 (X= I Br, CI). At room
temperature, the ionic conductivity increases linearly with increasing the radius of the
halogen ion and it is associated with the higher polarizability of the larger ions [84].
Similarly, MI, -
(M= Cd, Hg, Pb) glasses showed rapid rise in conductivity with the
introduction of 1- [85]. Silver based chalcogenides ADX, (X= Se, Te, etc.) were also
Fig. 1.3. (a) Structure of a-Agl and (b) silver ion mxpancy sites in a-Agl
synthesized and found to have high conductivity. In general. sulfide glasses exhibit more
conductivity than that of their corresponding oxide glasses [86]. Quaternary silver based
compounds are prepared to enhance the ionic conductivity following the pioneering work
by Chiobelli et al. Some of the silver ion conducting glasses is summarized in Table 1.3.
Fig 1.4 shows the temperature dependence of conductivity of some silver ion conducting
glasses [87- 1031.
Table 1. 3. Silver ion conducting glasses and their conductivity
Silver ion conducting glasses
Temperature (K)
Agl-ADS-AgPO3
Conductivity
(scm.')
5 . 7 0 10
~ '
303
I
298
I
%.Ox 1
or'
Fig. 1. 4. Log oT vs. 1000iT plots of silver based SIC glassy systems
1.7. Models for Ion Transport in Glasses
The understanding of ion transport in glassy electrolytes appears to be even less
developed than that in crystalline conductors, which, is largely due to lack of the complete
structural informations related to ion transport. Different superionic conducting glasses
exhibit different structural motifs and oversimplification of transport mechanism is
difficult. Reviews on various transport models of superion conducting glasses are available
and some of the models are explained in this section.
1 . 7 . 1 . Anderson and Stuart model
Anderson and Stuart proposed that the carrier ion is intrinsically mobile and the
activation energy is the sum of the energy required overcoming thc electrostatic forces and
strain component. They found the expression for the two energies and predicted the
activation energy for the diffusion of mobile ion in number of silicate glasses [104. 1051.
1. 7.2. Random site model
In this model, all the ions of particular type are treated as potential carriers with a
Gaussian distribution of activation energy. The ion mobility varies with distribution of
activation energy and thereby with glass composition. Generally, the variation of carrier
concentration with glass composition is relatively small and hence, the conductivity
variation with glass composition is controlled by change in ion mobility. This model
successfully explained the conductivity dependence on composition in fluorite structured
solid solutions [106, 1071.
1.7.3. Weak electrolyte model
Ravaine and Souquet [log, 1091 developed the weak electrolyte model. This has
been applied to the conductivity studies of NazO-SiOz glassy systems. In this system,
dissociated ions are assumed to occupy interstitial sites in the glassy network, while the
associated ions are located at non-bridging. When alkali oxide is incorporated with silica,
the bonds are broken. In these glasses, the ionic conductivity is found to vary considerably
with alkali oxide contents. The variation of ionic conductivity with NazO content was
explained due to variation of concentration of mobile ~ a ions.
'
1.7.4. Diffusion path model
Difision path model depends on potentials seen by the Ag' ions with oxygen and
iodide ions. The camer concentration depend on how many Ag' ions are located in the
shallow potential and mobility depends on how long the shallow wells are connected for a
long period, they form a favorable path for ion transport. This type of path is called
diffusion path and the model is called diffusion path model. In the glasses, diffusion path
can be formed more easily, since the configuration freedom is maximum in the disordered
system [I 10-1 121.
1. 7. 5. Diffusion controlled relaxation (DCR) model
S. R. Elliott and 8.B. Owens proposcd the diffusion controlled relaxation (DCR)
model for the microscopic transport mechanism of ions in glasses. According to this
model, there are energetically stable sites for the mobile ions to reside in the oxide glassy
structure. Ionic transport occurs by means of diffusive motion between the equivalent sites
resulting in the primary relaxational event with a characteristic microscopic relaxation
time. However, when a cation hops into one of the vicinal equivalent sites will result in the
creation of double occupancy known as interstitial effect on instantaneous relaxation
process [ l l 3 , 1141.
1.8. A p p l i c a t i o n s o f S u p e r i o n i c C o n d u c t o r s
The development of ionic technologies known as solid state ionics (SSI)was first
introduced by prof. T. Takehashi [I 151. The first developed ionic device was used for the
determination of thermodynamic oxygen ion conductivity at the high temperature [I 151191. In 1967, the Ford Motor company workers of Kummer and Yao had introduced the
sodium P-Alumina for making high energy density battery [120]. SIC materials are widely
used in the following fields.
(i). Thermodynamic studies
(ii). Diffusion coefficient measurement in solids / liquids
(iii). Sensors and partial pressure gauges
(iv). Fuel cells
(vi). Decomposition of gases
(vii). Oxidation catalysts
(viii). Coulometers
(ix). Electro chemical capacitors
(x). Electro chromic displays
(xi). Solid electrolyte thermometers
(xii). Thermoelectric generators
(xiii). Solid state batteries, etc.
Examples of various applications of solid electrolytes arc given Table. 1.4.
Table.] .4. Some examples of solid electrolytes with various applications
/
No.
I
Solid Electrolytes
I
Applications
LiAIF4 and LiNbO3
Windows
Agl-A@O-W03 with LaFx
Oxygen sensor
4.
Li l
Micro Battery
5.
Agl-Ago-WO3
Chemical sensor
1
1.9. Present Research Work
The present investigation is aimed at preparation by a melt quench, characterization
by XRD, FTIR, DSC, transport studies through impedance, mobility, polarization
measurements and solid state battery applications of three different sets of new quaternary
silver based SIC glassy compounds. The following combinations of glassy systems are
undertaken and studied.
Svstems
Names
(i). Agl - Ag2O - [As205-Te02]Silverarsenotellurite (SAT)
Process
Melt quench
(ii). AgI - Ag20- [Pz05-Te02] Silverphosphotellurite (SPT) Melt quench
(iii). AgI - Ag20- [V2O5-TeOz] Silve~anadotellurite(SVT) Melt quench
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