Powders and pellets of new NASICON compositions have been synthesized using
a mixed inorganic-organic sol-gel synthesis, by the preliminary formation
of a pre-hydrolized TEOS xerogel. The investigated compositions can be desc
ribed by the general formula Na3Zr2-(x/4)Si2-xP1+xO12, obtained by keeping
the Na concentration constant (= 3) at the optimum value reported for ionic
conductivity, with x = 0 (the usual NASICON composition), 0.667, and 1.333
. The xerogels were calcined at various temperatures in the range 400-1200
degreesC. The powder samples were analyzed by TG/DTA, BET measurements, XRD
, and SEM. The powders calcined at 500 degreesC were sintered into pellets
at 1100 degreesC for 6 h. The sintering behavior of the pellets was investi
gated by dilatometric measurements and SEM observations. The sinterability
increased with increasing x value. Dense samples of the new compositions we
re obtained by sintering at only 1100 degreesC. This is attributed to the o
ccurrence of liquid phase sintering. The electrical conductivity of the NAS
ICON sintered bodies was measured by ac impedance spectroscopy. The conduct
ivity decreased with decreasing c(0) lattice parameter of the hexagonal str
ucture or increasing x value. The CO2 gas sensors, using as electrolyte the
dense samples of the new NASICON compositions, showed good EMF response th
at was very close to the theoretical value, even for the sample with x = 1.
333 that showed much lower conductivity.