ABSTRACT
The structure of crystalline and amorphous materials in the sodium (Na) super-ionic conductor system Na1+xAlxGe2-x(PO4)3 with x = 0, 0.4, and 0.8 was investigated by combining (i) neutron and x-ray powder diffraction and pair-distribution function analysis with (ii) 27Al and 31P magic angle spinning (MAS) and 31P/23Na double-resonance nuclear magnetic resonance (NMR) spectroscopy. A Rietveld analysis of the powder diffraction patterns shows that the x = 0 and x = 0.4 compositions crystallize into space group-type R3Ì, whereas the x = 0.8 composition crystallizes into space group-type R3Ìc. For the as-prepared glass, the pair-distribution functions and 27Al MAS NMR spectra show the formation of sub-octahedral Ge and Al centered units, which leads to the creation of non-bridging oxygen (NBO) atoms. The influence of these atoms on the ion mobility is discussed. When the as-prepared glass is relaxed by thermal annealing, there is an increase in the Ge and Al coordination numbers that leads to a decrease in the fraction of NBO atoms. A model is proposed for the x = 0 glass in which super-structural units containing octahedral Ge(6) and tetrahedral P(3) motifs are embedded in a matrix of tetrahedral Ge(4) units, where superscripts denote the number of bridging oxygen atoms. The super-structural units can grow in size by a reaction in which NBO atoms on the P(3) motifs are used to convert Ge(4) to Ge(6) units. The resultant P(4) motifs thereby provide the nucleation sites for crystal growth via a homogeneous nucleation mechanism.
ABSTRACT
In this study, we synthesize glass-ceramics of the new Na1+xGe2(SiO4)x(PO4)3-x NASICON (Na super-ionic conductor) series to evaluate the effect of Si4+/P5+ substitution on the structural, microstructural, and electrical properties of the NaGe2(PO4)3 system. From X-ray diffraction, the presence of the NASICON phase is confirmed in all glass-ceramics. An expansion of the unit cell volume suggesting an increase in the bottleneck of the NASICON structure is also observed. Impedance spectroscopy allowed the separation of grain and grain boundary contributions. We observe that the grain conductivity is higher than the specific grain boundary conductivity in all of the investigated compositions (0 ≤ x ≤ 0.8). The Si4+/P5+ substitution causes an enhancement of about 2 and 3 orders of magnitude in the grain and specific grain boundary conductivities, respectively. This behavior is attributable to the introduction of new charge carriers (Na+) in the NASICON structure and a decrease in the activation energy. Finally, the lowest activation energy for grain (0.586 eV) is observed in the x = 0.6 sample, which indicates the easiest displacement of ions in the investigated series, suggesting that this composition presents the most suitable bottleneck size for (Na+) sodium ion conduction.
