Li-Ion Conductivity and Phase Stability of Ca-Doped LiBH4under High Pressure.
The effect of Ca doping on the Li-ion conductivity and phase stability of the rock-salt-type LiBH4phase emerging under high pressures in the range of gigapascals has been investigated. In situ electrochemical measurements under high pressure were performed using a cubic-anvil-type apparatus. Ca doping drastically enhanced the ionic conductivity of the rock-salt-type phase: the ionic conductivity of undoped and 5 mol %Ca-doped LiBH4was 2.2 × 10-4and 1.4 × 10-2S·cm-1under 4.0 GPa at 220 °C, respectively. The activation volume of LiBH4-5 mol %Ca(BH4)2, at 3.2 cm3·mol-1, was comparable to that of other fast ionic conductors, such as lithium titanate and NASICONs. Moreover, Ca-doped LiBH4showed lithium plating-stripping behavior in a cyclic voltammogram. These results indicate that the conductivity enhancement by Ca doping can be attributed to the formation of a LiBH4-Ca(BH4)2solid solution; however, the solid solution decomposed into the orthorhombic LiBH4phase and the orthorhombic Ca(BH4)2phase after unloading the high pressure.
Department of Materials Science, Graduate School of Engineering, Tohoku University , Sendai 980-8579, Japan.
Takeya
T
Mezaki
Yota
Y
Kuronuma
Department of Materials Science, Graduate School of Engineering, Tohoku University , Sendai 980-8579, Japan.
Itaru
I
Oikawa
Atsunori
A
Kamegawa
Department of Materials Science, Graduate School of Engineering, Tohoku University , Sendai 980-8579, Japan.
Hitoshi
H
Takamura