Li + ion doping into KI-KBH 4 solid solvent systems: The role of the BH 4 − anion
Li + ion doping into KI-KBH 4 solid solvent systems: The role of the BH 4 − anion
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DOI：
10.1016/j.jallcom.2017.11.244
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发表时间：
2018-02
影响因子：
6.2
通讯作者：
R. Miyazaki;Yasuto Noda;H. Miyazaki;K. Soda;T. Hihara
中科院分区：
文献类型：
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作者：
R. Miyazaki;Yasuto Noda;H. Miyazaki;K. Soda;T. Hihara
为了阐明BH4−阴离子对KI-KBH4固体溶剂体系中Li+离子掺杂的影响，分别控制固体溶剂中Li+和BH4−离子的浓度。证实了LiI溶解到KI-KBH4固体溶剂中，而如果固体溶剂中没有BH4−阴离子，则无法实现KI和LiI之间固溶体的形成。对于掺杂 10 mol% BH4−离子 (9KI·KBH4) 的固体溶剂，LiI 的溶解量高达 6 mol%。当Li+离子掺杂时，KI-KBH4系统的晶格参数增加。溶解有 LiI 的 KI-KBH4 体系的 7Li MAS-NMR 谱在 -0.72 ppm 处显示出一个共振峰，其位置与 LiI 的共振峰（-4.57 ppm）有很大不同。这些结果表明，掺杂的Li+离子不会简单地取代主体K+离子，而是占据KI-KBH4固体溶剂的间隙位置。同步辐射X射线粉末衍射测量的Rietveld分析结果表明，K+空位是通过间隙Li+离子作为电荷平衡而引入的。
In order to clarify the effect of BH4−anions on the Li+ion doping into the KI-KBH4solid solvent systems, the concentrations of the Li+and BH4−ions in a solid solvent were separately controlled. The dissolving of LiI into the KI-KBH4solid solvent was confirmed, while the formation of a solid solution between KI and LiI was not realized without the BH4−anions in the solid solvent. For the solid solvent doped with 10 mol% BH4−ions (9KI·KBH4), LiI could dissolve up to 6 mol%. The lattice parameters of the KI-KBH4systems increased when the Li+ions were doped. The7Li MAS-NMR spectrum for the KI-KBH4system dissolved with LiI showed one resonance peak at −0.72 ppm whose position is quite different from that for LiI (−4.57 ppm). These results indicated that the doped Li+ions would not simply substitute the host K+ions, but occupy the interstitial sites of the KI-KBH4solid solvent. The results of the Rietveld analysis of the synchrotron radiation X-ray powder diffraction measurements showed that K+vacancies are introduced by the doing of the interstitial Li+ions as a charge balance.