Phase-field determination of NaSICON materials in the quaternary system Na2O-P2O5-SiO2-ZrO2: II. Glass-ceramics and the phantom of excessive vacancy formation

This work focuses on a very narrow region in the quaternary system Na2O-P2O5-SiO2-ZrO2 to explore the occasionally proposed deficiency in zirconium and oxygen content of Na+ super-ionic conductor (NaSICON) materials. In addition, this region is known for the formation of glass-ceramics, but a systematic study of such materials has not been carried out yet. For this purpose, 2 series of compositions were defined and synthesized: Na3.4Zr2-3x/4Si2.4-x/4P0.6+x/4O12-11x/8 and Na3.4Zr2-3x/4Si2.4+x/4P0.6+1.5x/4O12-x/16. They only differ in the silicate and phosphate content. In the first series the molar content is constant, nSi + nP = 3. The latter series allows an excess of the 2 cations to meet the composition Na3.1Zr1.55Si2.3P0.7O11 or alternatively re-written as Na3.4Zr1.7Si2.52P0.77Ol2, which was formerly regarded as a superior material to the frequently reported composition Na3Zr2Si2POl2.Several characterization techniques were applied to better understand the relationships between phase formation, processing, and properties of the obtained glass ceramics in the context of the quasi-quaternary phase diagram. The investigations gave clear evidence that a glass phase is progressively formed with increasing x. Therefore, compounds with x > 0.2 have to be regarded as glass-ceramic composites. The resulting NaSICON materials revealed a very limited Zr deficiency with charge compensation by Na ions and a non-detectable amount of oxygen vacancies verified by neutron scattering and atomistic simulations.Hence, this work is the first systematic investigation of pretended Zr-deficient NaSICON materials, which clearly show the chemistry of a 2-phase region. The 2 investigated series are directed toward a region that is orthogonal to the series Na3Zr3-ySi2PyO11.5+y/2 reported in the first part of this series of publications.