期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 121, 期 35, 页码 19010-19021出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.7b04905
关键词
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资金
- People Program (Marie Curie Actions) of the European Union's Seventh Framework Program FP7/under REA [607040]
- Danish National Research Foundation, Center for Materials Crystallography [DNRF93]
- Innovation Fund Denmark (project HyFill-Fast)
- Danish Research Council for Nature and Universe (Danscatt)
- HyNanoBorN project
- Funhy (NordForsk) project
- Carlsberg Foundation
- Swiss National Science Foundation
In this work, a new type of addition reaction between La(BH4)(3) and LiX, X = Cl, Br, I, is used to synthesize LiLa(BH4)(3)Cl and two new compounds LiLa(BH4)3X, X = Br, I. This method increases the amounts of LiLa(BH4)(3)X and the sample purity. The highest Li-ion conductivity is observed for LiLa(BH4)(3)Br, 7.74 x 10(-5) S/cm at room temperature (RT) and 1.8 x 10(-3) S/cm at 140 degrees C with an activation energy of 0.272 eV. Topological analysis suggests a new lithium ion conduction pathway with two new different types of bottleneck windows. The sizes of these windows reveal an opposite size change with increasing lattice parameter, that is, increasing size of the halide ion in the structure. Thus, we conclude that the sizes of both windows are important for the lithium ion conduction in LiLa(BH4)(3)X compounds. The lithium ion conductivity is measured over one to three heating cycles and with different contacts (gold or carbon) between the electrodes and the electrolyte. Moreover, B-11 MAS NMR is used to verify the contents of the samples, whereas thermogravimetric analysis shows 4.8 and 3.6 wt % of hydrogen release for LiLa(BH4)(3)Cl and LiLa(BH4)(3)Br in the temperature range RT to 400 degrees C.
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