Ionic conductivity of the Na1+xM x III Zr2?x(PO4)3 systems (M = Al,Ga, Cr,Fe, Sc,In, Y,Yb)

The existence and ionic conductivity of solid solutions Na_1+xM _x ^III Zr_2–x(PO₄)₃ with Nasicon-like structure have been investigated and the results compared with literature data. A limited range of solid solutions is formed with M^III = aluminium, gallium, yttrium, ytterbium, whereas a continuous series is obtained for M^III = chromium, iron, scandium, indium. The pure end member Na₃ln₂(PO₄)₃ is reported for the first time; according to powder diffraction data, it is hexagonal witha = 0.8966(1) andc = 2.2104(4) nm. The small monoclinic distortion already known for M^III = chromium, iron and scandium is restricted tox values very close to 2. Ionic conductivity measurements show that for a given value ofx, the mobility of the Na⁺ ions is strongly influenced both by the ionic radius and the type of electronic structure of the M^III ion. However, no simple correlation can be found.