A Synthesis and Crystal Chemical Study of the Fast Ion Conductor Li7鈥?xGaxLa3 Zr2O12 with x = 0.08 to 0.84

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• 作者：Daniel Rettenwander ; Charles A. Geiger ; Martina Tribus ; Peter Tropper ; Georg Amthauer
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：June 16, 2014
• 年：2014
• 卷：53
• 期：12
• 页码：6264-6269
• 全文大小：353K
• 年卷期：v.53,no.12(June 16, 2014)
• ISSN：1520-510X

文摘

Fast-conducting phase-pure cubic Ga-bearing Li₇La₃Zr₂O₁₂ was obtained using solid-state synthesis methods with 0.08 to 0.52 Ga³⁺ pfu in the garnet. An upper limit of 0.72 Ga³⁺ 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 ⁷¹Ga MAS NMR spectroscopy. The unit-cell parameter, a₀, of the various garnets does not vary significantly as a function of Ga³⁺ content, with a value of about 12.984(4) 脜. Full chemical analyses for the solid solutions were obtained giving: Li_7.08Ga_0.06La_2.93Zr_2.02O₁₂, Li_6.50Ga_0.15La_2.96Zr_2.05O₁₂, Li_6.48Ga_0.23La_2.93Zr_2.04O₁₂, Li_5.93Ga_0.36La_2.94Zr_2.01O₁₂, Li_5.38Ga_0.53La_2.96Zr_1.99O₁₂, Li_4.82Ga_0.60La_2.96Zr_2.00O₁₂, and Li_4.53Ga_0.72La_2.94Zr_1.98O₁₂. The NMR spectra are interpreted as indicating that Ga³⁺ mainly occurs in a distorted 4-fold coordinated environment that probably corresponds to the general 96h crystallographic site of garnet.