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Ionic conductors

Ionic solids contain defects that allow the migration of ions in an electric field Some solid materials have very high ionic conductivities at reasonable temperatures
useful in solid state devices

mobile vacancy

mobile interstitial

Applications of solid ionic conductors


Membranes in separation processes Electrolytes in sensors Electrolytes in fuel cells and batteries
should be a poor electronic conductor

Electrode materials in solid state batteries


should be a good electronic and ionic conductor

Factors effecting the conductivity


=nZe Conductivity is influenced by 1)the carrier concentration n, 2) the carrier mobility Usually, defects act as the charge carriers
not many defects in most ionic solids mobility is usually low at room temperature Material Ionic conductors Ionic crystals Solid Electrolytes Liquid electrolytes Electronic conductors Metals Semiconductors Insulators Conductivity (S m-1) < 10-16 10-2 10-1-103 10-1-103 103-107 10-3-104 < 10-10

Ionic conductivity in NaCl


NaCl is a poor ionic conductor Conduction involves migration of cation vacancies Cation vacancies are present due to
doping - extrinsic defects Schottky defects - intrinsic defects

Conduction is an activated process


= 0 exp (-Ea/kT) - Arrhenius equation

Temperature dependence of conductivity


= (0/T) exp(-Ea/kT)
Contribution from mobility and defect formation

Idealized conductivity for NaCl

At low T conductivity is dominated by mobility of extrinsic defects At High T, conductivity is due to thermally formed (intrinsic) defects

Intrinsic versus extrinsic conductivity


Extrinsic conductivity
= (0/T) exp(-Ea/kT) carrier concentration is fixed by doping

Intrinsic conductivity
carrier concentration varies with temperature = (0/T) exp(-Ea/kT) exp(-HS/2kT) slope of plot gives Ea + HS/2

Cation vacancy migration mechanism


Cations can not hop from site to site via a direct route
not enough space

Cations migrate via an interstitial site


this is a tight squeeze and requires energy

Experimental conductivity of NaCl


Broadly as expected
Get deviation at low T due to vacancy pairing Get deviation at high T due to screening of mobile defects by defects of opposite charge
Debye-Huckle type model

Energetics of ionic conduction in NaCl


Process Migrationof Na+, Em Migration of ClFormation of Schottky pair Dissociation of vacancy pair Dissociation of vacancy Mn2+ pair Activation energy (eV) 0.65-0.85 0.90-1.10 2.18-2.38 ~1.3 0.27-0.50

AgCl
The predominant defect in AgCl is cation Frenkel Cation interstitials are more mobile than cation vacancies Cation interstitials can migrate by one of two mechanisms
direct movement indirect movement

Migration mechanism in AgCl


Two possible pathways for interstitial migration: 1) move directly from interstitial to interstitial 2) interstitial displaces regular cation onto interstitial position Migration actually occurs by second pathway

Evidence for the indirect mechanism


Both charge and mass transport through a crystal can be measures
conductivity gives charge mobility diffusion measurements using radiolabelled Ag+ gives mobility of Ag+

Charge is transported twice as fast as Ag+ ions suggesting the indirect mechanism is correct

Doping in AgCl
Doping AgCl with a divalent impurity like Cd2+ reduces the ionic conductivity of the specimen There is an equilibrium between cation vacancies and Ag+ interstitials
doping increases vacancy concentration doping decreases interstitial concentration

Cd2+ doped AgCl


Schematic showing effect of Cd2+ impurity on conductivity Presence of Cd2+ reduces number of Ag+ interstitials and hence lowers conductivity

Get minimum in conductivity curve when doped at high impurity concentrations conductivity is dominated by cation vacancy migration, at low concentrations interstitial migration dominates

Solid electrolytes
There is a technological need for solids that have very high ionic conductivities Such materials are referred to as FAST ION CONDUCTORS They include:
AgI Na alumina NASICON, Na1+xZr2[(PO4)3-x(SiO4)x] Stabilized zirconias

Ionic conductivity of some good solid electrolytes

=- alumina
Na1+xAl11O17+x/2 () and Na1+xMgxAl11-xO17 () are good sodium ion conductors at moderate temperatures Na ions have high mobility and can be ion exchanged with a wide variety of other cations M2O.x Al2O3 x = 5 - 11
M = Alkali+, Cu+, Ag+, Ga+, In+, Tl+, NH4+ x = 5-7 usually produces material x = 8 - 11 gives material material usually stabilized by addition of Li+ or Mg2+

The structures of and alumina

The structure of - alumina

Conduction plane of alumina

The sodium sulfur cell


Sodium sulfur cells have a high energy density
useful for electric vehicles

There are safety concerns


molten sodium

2Na(l) --> 2Na+ + 2e2Na+ + 5S(l) + 2e- ----> Na2S5(l)

Sodium sulfur phase diagram


Need to operate at high temperatures Can not fully discharge cell (solidifies)

Silver iodide
At low temperatures AgI adopts either a Wurtzite or zinc blende structure
Ag+ fills half of the tetrahedral holes in a close packed I- array

Above 146o C it transforms to a BCC structure with the Ag+ filling a small fraction of the available tetrahedral sites
the cation sublattice melts ~ 130 Sm-1

The structure of - AgI

Cation sites in =- AgI

Ionic conduction in =- AgI


There are many possible sites for Ag+
12 tetrahedral 24 trigonal 6 octahedral

There are only 2 Ag+ ions per unit cell!


these ions are found disordered on the tetrahedral sites

Motion between sites is facile


~0.05 eV activation barrier

RbAg4I5
AgI is polymorphic. The high temperature phase has a high ionic conductivity associated with a melted Ag+ sublattice
At low T ionic conductivity drops RbAg4I5 discovered while trying to find materials that still had AgI structure at low T

RbAg4I5
Highest room temperature ionic conductivity of any crystalline solid, 0.25 S cm-1
Not stable < ~25 C

Cu2HgI4
Material shows an order disorder phase transition similar to AgI
color change at phase transition marked increase in ionic conductivity at phase transition

Structure has FCC array of I- with cations filling tetrahedral holes


at low T cations are ordered at high T they are disordered over all sites

The structure of Cu2HgI4 at low T

Stabilized zirconias
Y2O3 and CaO can be dissolved in ZrO2
creates a lot of oxygen vacancies

At high temperatures the defects are mobile


oxide ion conductor

Applications of stabilized zirconia


Oxide conductors are of use for
oxygen sensors
based on concentration cell, can be used to measure O2 in exhaust gases, molten metals

fuel cell membranes

ZrO2 is only usable at high temperatures

An oxygen sensor
An O2 concentration cell can be built E = [2.303RT/4F] log(p/pref)

Fuel cells
Fuel cells are devices for the direct conversion of fuels such as CH3OH, H2, CO to electrical energy

Solid oxide fuel cells


Fuel cells offer an efficient and clean way of using fossil fuels, but
high cost thermal cycling problems

Solid oxide fuel cell performance

from a paper by S.C. Singhal in Proceedings of the Fourth International Symposium on Solid Oxide Fuel Cells, 1995

Electrochromic devices
Color changes such as those needed in smart windows can be achieved by moving ions into a suitable solid

Lithium batteries
Batteries based on lithium are attractive as they can be light a have a very high voltage output
Considerable current research on cathodes and electrolytes for these devices