Solid state chemistry文档[精品].pptVIP

SOLID ELECTROLYTES Defects and non-stoichiometry If storage batteries can be made to give sufficient power and they are light, they become useful as alternative fuel sources - to power cars for instance; we will look in some detail at the development of the sodium-sulphur battery for this purpose. To take a simple example, LiI, although it has a fairly low ionic conductivity (Figure 5.7), is used in the manufacture of the batteries that are used in heart pace-makers: LiI is the solid electrolyte that separates the anode (lithium) from the cathode (iodine embedded in a conducting polymer). The cell reaction is: * SOLID ELECTROLYTES Defects and non-stoichiometry anode: 2Li(s) = 2Li+ + 2e- cathode: I2(s) + 2e- = 2I- overall: 2Li(s) + I2(s) = 2LiI(s) Because the LiI contains Schottky defects, the small Li+ cations are able to pass through the solid electrolyte, while the released electrons go round an external circuit. Fast-ion conductors Some ionic solids have been discovered that have a much higher conductivity than is typical for such compounds and these are known as fast-ion conductors. One of the earliest to be noticed, in 1913 by Tubandt and Lorenz, was a high-temperature phase of silver iodide. * Defects and non-stoichiometry SOLID ELECTROLYTES Below 146oC there are two phases of AgI: γ-AgI, which has the zinc blende structure, and β-AgI with the wurtzite structure; both are based on a close-packed array of iodide ions with half of the tetrahedral holes filled. However, above 146oC a new phase, α-AgI, is observed where the iodine ions now have a body-centred cubic lattice. A dramatic increase in conductivity is observed for this phase (Figure 5.7): the conductivity of α-AgI is very high, 131Sm-1, a factor of 104 higher than that of β- or γ-AgI, comparable with the conductivity of the best conducting liquid electrolytes. * SOLID ELECTROLYTES Defects and non-stoichiometry The explanation lies in the crystal structure of u-Agl. The structure is b