Li-Ion Conductivity and Phase Stability of Ca-Doped LiBH4 under High Pressure

Takeya Mezaki, Yota Kuronuma, Itaru Oikawa, Atsunori Kamegawa, Hitoshi Takamura

Research output: Contribution to journalArticlepeer-review

19 Citations (Scopus)


The effect of Ca doping on the Li-ion conductivity and phase stability of the rock-salt-type LiBH4 phase 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 LiBH4 was 2.2 × 10-4 and 1.4 × 10-2 S·cm-1 under 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 LiBH4 showed 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)2 solid solution; however, the solid solution decomposed into the orthorhombic LiBH4 phase and the orthorhombic Ca(BH4)2 phase after unloading the high pressure.

Original languageEnglish
Pages (from-to)10484-10489
Number of pages6
JournalInorganic chemistry
Issue number20
Publication statusPublished - 2016 Oct 17

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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