TY - JOUR
T1 - Synthesis, Crystal Structure, and Stability of Cubic Li7-xLa3Zr2-xBixO12
AU - Wagner, Reinhard
AU - Rettenwander, Daniel
AU - Redhammer, Günther J.
AU - Tippelt, Gerold
AU - Sabathi, Gebhard
AU - Musso, Maurizio E.
AU - Stanje, Bernhard
AU - Wilkening, Martin
AU - Suard, Emmanuelle
AU - Amthauer, Georg
PY - 2016/12/5
Y1 - 2016/12/5
N2 - Li oxide garnets are among the most promising candidates for solid-state electrolytes in novel Li ion and Li metal based battery concepts. Cubic Li7La3Zr2O12 stabilized by a partial substitution of Zr4+ by Bi5+ has not been the focus of research yet, despite the fact that Bi5+ would be a cost-effective alternative to other stabilizing cations such as Nb5+ and Ta5+. In this study, Li7-xLa3Zr2-xBixO12 (x = 0.10, 0.20, ..., 1.00) was prepared by a low-temperature solid-state synthesis route. The samples have been characterized by a rich portfolio of techniques, including scanning electron microscopy, X-ray powder diffraction, neutron powder diffraction, Raman spectroscopy, and 7Li NMR spectroscopy. Pure-phase cubic garnet samples were obtained for x ≥ 0.20. The introduction of Bi5+ leads to an increase in the unit-cell parameters. Samples are sensitive to air, which causes the formation of LiOH and Li2CO3 and the protonation of the garnet phase, leading to a further increase in the unit-cell parameters. The incorporation of Bi5+ on the octahedral 16a site was confirmed by Raman spectroscopy. 7Li NMR spectroscopy shows that fast Li ion dynamics are only observed for samples with high Bi5+ contents.
AB - Li oxide garnets are among the most promising candidates for solid-state electrolytes in novel Li ion and Li metal based battery concepts. Cubic Li7La3Zr2O12 stabilized by a partial substitution of Zr4+ by Bi5+ has not been the focus of research yet, despite the fact that Bi5+ would be a cost-effective alternative to other stabilizing cations such as Nb5+ and Ta5+. In this study, Li7-xLa3Zr2-xBixO12 (x = 0.10, 0.20, ..., 1.00) was prepared by a low-temperature solid-state synthesis route. The samples have been characterized by a rich portfolio of techniques, including scanning electron microscopy, X-ray powder diffraction, neutron powder diffraction, Raman spectroscopy, and 7Li NMR spectroscopy. Pure-phase cubic garnet samples were obtained for x ≥ 0.20. The introduction of Bi5+ leads to an increase in the unit-cell parameters. Samples are sensitive to air, which causes the formation of LiOH and Li2CO3 and the protonation of the garnet phase, leading to a further increase in the unit-cell parameters. The incorporation of Bi5+ on the octahedral 16a site was confirmed by Raman spectroscopy. 7Li NMR spectroscopy shows that fast Li ion dynamics are only observed for samples with high Bi5+ contents.
UR - http://www.scopus.com/inward/record.url?scp=85002202372&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.6b01825
DO - 10.1021/acs.inorgchem.6b01825
M3 - Article
AN - SCOPUS:85002202372
SN - 0020-1669
VL - 55
SP - 12211
EP - 12219
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 23
ER -