Identification of the Dehydrogenated Product of Ca(BH4)(2)

Abstract

We have investigated the decomposition path and reversibility of Ca(BH4)(2) and Ca(BH4)(2) + MgH2 composite using X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, and Raman spectroscopy. Formation of CaB6 during dehydrogenation of both systems was confirmed for the first time. CaB6 appears as broad peaks in X-ray diffraction data, but Raman spectroscopy unambiguously captures the existence of CaB6. Reversibility of catalyzed Ca(BH4)(2) was previously reported, and here we demonstrate reversibility of Ca(BH4)(2) + MgH2 composite. Dehydrogenated product of Ca(BH4)(2) + MgH2 is composed of CaH2, CaB6, and Mg. About 60% reversibility was achieved after rehydrogenation for 24 h under 90 bar of hydrogen pressure at 350 degrees C even without the help of catalysts, which makes a good contrast with the case of pure Ca(BH4)(2) where almost negligible rehydrogenation occurs under the same conditions. To understand the difference, the role of Mg in rehydrogenation is worth further investigation. Formation of CaB6 seems critical in the reversibility of Ca(BH4)(2) containing systems; the case of other borohydrides is compared.