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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
σ=nZeµ Conductivity is influenced by 1)the carrier concentration n, 2) the carrier mobility µ 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 µ = µ0 exp (-Ea/kT) .Arrhenius equation Temperature dependence of conductivity σ = (σ0/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 – σ = (σ0/T) exp(-Ea/kT) – carrier concentration is fixed by doping Intrinsic conductivity – carrier concentration varies with temperature – σ = (σ’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 .

10 2.65-0.50 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 .85 0. Em Migration of ClFormation of Schottky pair Dissociation of vacancy pair Dissociation of vacancy – Mn2+ pair Activation energy (eV) 0.18-2.27-0.38 ~1.90-1.3 0.Energetics of ionic conduction in NaCl Process Migrationof Na+.

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 .

at low concentrations interstitial migration dominates .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.

Na1+xZr2[(PO4)3-x(SiO4)x] Stabilized zirconias Ionic conductivity of some good solid electrolytes .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: – – – – α AgI Na β alumina NASICON.

Ga+.alumina Na1+xAl11O17+x/2 (β) and Na1+xMgxAl11-xO17 (β”) 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. In+. NH4+ x = 5-7 usually produces β” material x = 8 .11 – – – – M = Alkali+.11 gives β material β” material usually stabilized by addition of Li+ or Mg2+ The structures of β and β” alumina . Cu+. Ag+.β=. Tl+.x Al2O3 x = 5 .

The structure of β .alumina Conduction plane of β 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.AgI .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” σ ~ 130 Sm-1 The structure of α .

Cation sites in α=.05 eV activation barrier .AgI Ionic conduction in α=.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.

0.25 S cm-1 – Not stable < ~25 °C .RbAg4I5 AgI is polymorphic. The high temperature α 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 α – AgI structure at low T RbAg4I5 Highest room temperature ionic conductivity of any crystalline solid.

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 .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.

can be used to measure O2 in exhaust gases.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. molten metals … – fuel cell membranes ZrO2 is only usable at high temperatures .

An oxygen sensor An O2 concentration cell can be built E = [2. CO to electrical energy .303RT/4F] log(p’/pref) Fuel cells Fuel cells are devices for the direct conversion of fuels such as CH3OH. H2.

Singhal in Proceedings of the Fourth International Symposium on Solid Oxide Fuel Cells. but – high cost – thermal cycling problems Solid oxide fuel cell performance from a paper by S.C. 1995 .Solid oxide fuel cells Fuel cells offer an efficient and clean way of using fossil fuels.

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 .