Abstract
The Li+ ion conductor Li27-x [P4 O7+x N9-x ]O3 (x≈1.9) has been synthesized from P3 N5 , Li3 N and Li2 O in a Ta ampoule at 800 °C under Ar atmosphere. The cubic compound crystallizes in space group I 3d with a=12.0106(14) Å and Z=4. It contains both non-condensed [PO2 N2 ]5- and [PO3 N]4- tetrahedra as well as O2- ions, surrounded by Li+ ions. Charge neutrality is achieved by partial occupancy of Li positions, which was refined with neutron powder diffraction data. Measurements of the partial ionic and electronic conductivity show a total ionic conductivity of 6.6×10-8 S cm-1 with an activation energy of 0.46±0.02 eV and a bulk ionic conductivity of 4×10-6 S cm-1 at 25 °C, which is close to the ionic conductivity of amorphous lithium nitridophosphate. This makes Li27-x [P4 O7+x N9-x ]O3 an interesting candidate for investigation of structural factors affecting ionic conductivity in lithium oxonitridophosphates.
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