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@ARTICLE{Dashjav:1026279,
author = {Dashjav, Enkhtsetseg and Gerhards, Marie-Theres and Klein,
Felix and Grüner, Daniel and Hansen, Thomas C. and Rohrer,
Jochen and Albe, Karsten and Fattakhova-Rohlfing, Dina and
Tietz, Frank},
title = {{P}hase-field determination of {N}a{SICON} materials in the
quaternary system {N}a2{O}-{P}2{O}5-{S}i{O}2-{Z}r{O}2: {II}.
{G}lass-ceramics and the phantom of excessive vacancy
formation},
journal = {Next energy},
volume = {4},
issn = {2949-821X},
address = {[Amsterdam]},
publisher = {Elsevier},
reportid = {FZJ-2024-03358},
pages = {100130 -},
year = {2024},
abstract = {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.},
cin = {IEK-1 / IEK-2},
ddc = {333.7},
cid = {I:(DE-Juel1)IEK-1-20101013 / I:(DE-Juel1)IEK-2-20101013},
pnm = {1222 - Components and Cells (POF4-122)},
pid = {G:(DE-HGF)POF4-1222},
typ = {PUB:(DE-HGF)16},
UT = {WOS:001470144100002},
doi = {10.1016/j.nxener.2024.100130},
url = {https://juser.fz-juelich.de/record/1026279},
}