Professional Documents
Culture Documents
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
At low T conductivity is dominated by mobility of extrinsic defects At High T, conductivity is due to thermally formed (intrinsic) defects
Intrinsic conductivity
carrier concentration varies with temperature = (0/T) exp(-Ea/kT) exp(-HS/2kT) slope of plot gives Ea + HS/2
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
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
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
=- 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+
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
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
Stabilized zirconias
Y2O3 and CaO can be dissolved in ZrO2
creates a lot of oxygen vacancies
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
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