Ionic vs Electronic

Conduction in
Solids
Indroneil Kanungo
 Contents

1. Ionic Conductors
1.1. Introduction
1.2. Conduction Mechanisms
1.3. Classification
1.4. Properties
1.5. Applications
1.6. Experimental Techniques
2. Electronic Conductors
Ionic Conductors
The study of ionic conduction in solid state originated
way back in 1838 when Faraday discovered that
PbF2 and Ag2S are good conductors of electricity.

AgI is among the best ionic conductors with it’s

conductivity reaching 2.62 /Ohm-cm close to its
melting point.
There exist many solids with high ionic conductivity
(>10^–4 /Ohm-cm ) and they are of immense use in
diverse technological applications.

Some of these solids which are also good electronic

conductors are often referred to as ‘mixed
conductors’, while the term ‘superionic conductor’ or
‘fast ion conductor’ is reserved for good ionic
conductors with negligible electronic conductivity.

One of the most important use of superionic

conductors is, as electrolytes in battery applications
and hence, often, they are referred to as ‘solid
electrolytes’ as well.
Conduction Mechanisms
In order for an ion to move through a crystal
it must hop from an occupied site to a
vacant site. Thus ionic conductivity can only
occur if defects are present. The two
simplest types of point defects are
Schottky and Frenkel defects.
Ion Migration (Schottky Defects)

Na Cl
Cl Na E

Cl

Na Cl
 Ion Migration (Frenkel Defects)
The Frenkel defects in AgCl can migrate via two mechanisms.
Ag Cl Ag Ag Cl Ag
Cl Ag Cl Ag Cl
Cl
Ag1
Ag1
Cl Ag2 Cl Cl Ag2 Cl
Ag Cl Ag Ag Cl Ag
Direct Interstitial Jump
Ag Cl Ag Ag Cl Ag
Cl Ag Cl Ag Cl
Cl
Ag2
Ag1
Cl Ag2 Cl Cl Ag1 Cl
Ag Cl Ag Ag Cl Ag

Interstitialcy Mechanism
Classification
1. Based on the mobile species :
1.1. Anionic Conductors
1.1.1. Oxide Conductors
1.1.2. Fluoride Conductors
1.2. Cationic Conductors
1.2.1. Lithium Ion Conductor
1.2.2. Copper Ion Conductor
1.2.3. Beta - Alumina Conductor
1.2.4. Protonic Conductors
1.2.5. Silver Ion Conductors
2. Based on microstructure of solids :
2.1. Single/Polycrystalline
2.2. Amorphous/Glass
2.3. Composites
2.4. Polymers
Properties
 Anionic Conductors

Superionic conductors with negative ions as

charge carriers are called anionic conductors.
Anionic conductors do not exhibit good ionic
conductivity at ambient temperature.
 Oxide 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 (Ca2+, Y3+, Sr2+, etc. in
Hf02, Ge02 etc), which control the number of point
defects and their mobility.
 Fluoride 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.
 Cationic Conductors

In these, electrical conductivity is due to the

presence of positive ions as charge carriers are
called as cationic conductors.
 Lithium Ion Conductors

The ionic radius of lithium ion is small compared to

those of K+ and Rb+ ions. Hence, lithium
compounds have more conductivity than Na+ & K+
ion conductors. Lithium compounds are useful for
high energy density batteries due to their high
electrochemical potential.
 Beta Alumina Conductors

One of the most extensively studied classes of

superionic conductors is the group of materials
having the general formula : B2O.A2O3,
Where B=Na+, K+, Tl+, Rb+, Ag+, H3O+, etc.
And A=Al3+, Fe3+, 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.
 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.
Applications
Superionic conductors are used in a variety
of fields from Thermodynamic Study to fuel
cells. Among its among popular uses are
solid state batteries. They have a few
additional benefits over normal batteries
which have a liquid electrolyte.
Experimental Techniques
 Structural Characterization

Long range motion of ions along with a “smooth”

network of conduction chains lead to high ionic
conductivity. Hence, a detailed understanding of
the structural features is of particular importance in
the context of superionic conductors. As in the
case of other crystalline solids, X-ray and neutron
diffraction techniques are commonly employed to
elucidate the structure features of superionic
solids.
 Thermodynamic properties

Differential scanning calorimetry (DSC) as well as

differential thermal analysis (DTA) are useful in
deducing the thermodynamical properties of solids.
 Vibrational Spectra

Vibrational spectra of the solids have been

recorded using infrared (IR), far-infrared (FIR) or
Raman spectroscopy. These techniques are also
useful in characterizing superionic solids as the
frequencies associated with the diffusive modes of
the mobile ions are lower, a few tens in units of
cm–1.
 Conductivity, diffusion
coefficient and ion transport

The net conductivity of a solid has contributions

from electrons as well as ions. The transference
number measurements can be performed to find
out the actual charge carriers in a solid.
Comparison with Electronic
Conductors
Ionic Conductors Electronic Conductors

● Conductivity is in the order of ● Conductivity is in the order of

10^-4 - 10 mho/cm 10 - 10^7 mho/cm
● Conductivity decreases ● Conductivity increases
linearly as temperature exponentially with
increases. temperature.
References

● Ionic conduction in the solid state - P PADMA KUMAR and S

YASHONATH
● Springer Handbook of Electronic and Photonic Materials - Harry Tuller
● Theory of Ionic Conduction in Solids - L. Young
Thank You

Indroneil Kanungo