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Research for preparation of cation-conducting solids by high-pressure synthesis and other methods

It was shown that two body-centered-cubic skeleton structures, the Im3 KSbO3 phase and the defect-pyrochlore phase A(+)B2X6, do exhibit fast Na(+)-ion transport. The placement of anions at the tunnel intersection sites does not impede Na(+)-ion transport in (NaSb)3)(1/6 NaF), and may not in (Na(1+2x)Ta2 5F)(Ox). The activation energies are higher than those found in beta-alumina. There are two possible explanations for the higher activation energy: breathing of the bottleneck (site face or edge) through which the A(+) ions must pass on jumping from one site to another may be easier in a layer structure and/or A(+)-O bonding may be stronger in the cubic structures because the O(2-) ion bonds with two (instead of three) cations of the skeleton. If the former explanation is dominant, a lower activation energy may be achieved by optimizing the lattice parameter. If the latter is dominant, a new structural principle may have to be explored.

Goodenough, J. B.↗

Fast Na/+/-ion transport in skeleton structures

The skeleton structures considered in the investigations consist of a rigid subarray with an interconnected interstitial space in which ions move in three dimensions. The classes of skeleton structures investigated include the Im3 phase of high-pressure KSbO3, the defect-pyrochlore structure illustrated by RbMgAlF6, and the carnegieite structure of high-temperature NaAlSiO4. A description is given of the results obtained in transport measurements involving dense polycrystalline ceramic disks. Results obtained in the case of the Na(+)-ion transport in Na3Zr2PSi2O12 appear particularly promising concerning the possible use of such substances in solid-electrolyte applications.

Goodenough, J. B.↗