Rettenwander Daniel, Geiger Charles A, Tribus Martina, Tropper Peter, Amthauer Georg
Department of Materials Science and Physics, University of Salzburg , Hellbrunnerstrasse 34, A-5020 Salzburg, Austria.
Inorg Chem. 2014 Jun 16;53(12):6264-9. doi: 10.1021/ic500803h. Epub 2014 May 29.
Fast-conducting phase-pure cubic Ga-bearing Li7La3Zr2O12 was obtained using solid-state synthesis methods with 0.08 to 0.52 Ga(3+) pfu in the garnet. An upper limit of 0.72 Ga(3+) pfu in garnet was obtained, but the synthesis was accompanied by small amounts of La2Zr2O12 and LiGaO3. The synthetic products were characterized by X-ray powder diffraction, electron microprobe and SEM analyses, ICP-OES measurements, and (71)Ga MAS NMR spectroscopy. The unit-cell parameter, a0, of the various garnets does not vary significantly as a function of Ga(3+) content, with a value of about 12.984(4) Å. Full chemical analyses for the solid solutions were obtained giving: Li7.08Ga0.06La2.93Zr2.02O12, Li6.50Ga0.15La2.96Zr2.05O12, Li6.48Ga0.23La2.93Zr2.04O12, Li5.93Ga0.36La2.94Zr2.01O12, Li5.38Ga0.53La2.96Zr1.99O12, Li4.82Ga0.60La2.96Zr2.00O12, and Li4.53Ga0.72La2.94Zr1.98O12. The NMR spectra are interpreted as indicating that Ga(3+) mainly occurs in a distorted 4-fold coordinated environment that probably corresponds to the general 96h crystallographic site of garnet.
采用固态合成方法，在石榴石中引入0.08至0.52 Ga(3+) pfu，获得了快速传导的纯相立方含镓Li7La3Zr2O12。在石榴石中获得了0.72 Ga(3+) pfu的上限，但合成过程中伴有少量的La2Zr2O12和LiGaO3。通过X射线粉末衍射、电子微探针和扫描电子显微镜分析、电感耦合等离子体发射光谱测量以及(71)Ga固体核磁共振光谱对合成产物进行了表征。各种石榴石的晶胞参数a0随Ga(3+)含量的变化不显著，值约为12.984(4) Å。获得了固溶体的全化学分析结果：Li7.08Ga0.06La2.93Zr2.02O12、Li6.50Ga0.15La2.96Zr2.05O12、Li6.48Ga0.23La2.93Zr2.04O12、Li5.93Ga0.36La2.94Zr2.01O12、Li5.38Ga0.53La2.96Zr1.99O12、Li4.82Ga0.60La2.96Zr2.00O12和Li4.53Ga0.72La2.94Zr1.98O12。核磁共振光谱表明，Ga(3+)主要存在于扭曲的4重配位环境中，这可能对应于石榴石的一般96h晶体学位置。
