First-principles studies of phase stability and crystal structures in Li-Zn mixed-metal borohydrides

Yongli Wang*, Yongsheng Zhang, C. Wolverton

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations


We address the problem of finding mixed-metal borohydrides with favorable thermodynamics and illustrate the approach using the example of LiZn 2(BH4)5. Using density functional theory (DFT), along with the grand-canonical linear programming method (GCLP), we examine the experimentally and computationally proposed crystal structures and the finite-temperature thermodynamics of dehydrogenation for the quaternary hydride LiZn2(BH4)5. We find the following: (i) For LiZn2(BH4)5, DFT calculations of the experimental crystal structures reveal that the structure from the neutron diffraction experiments of Ravnsbæk is more stable [by 24 kJ/(mol f.u.)] than that based on a previous x-ray study. (ii) Our DFT calculations show that when using the neutron-diffraction structure of LiZn2(BH 4)5, the recently theoretically predicted LiZn(BH 4)3 compound is unstable with respect to the decomposition into LiZn2(BH4)5+LiBH4. (iii) GCLP calculations show that even though LiZn2(BH4)5 is a combination of weakly [Zn(BH4)2] and strongly (LiBH4) bound borohydrides, its decomposition is not intermediate between the two individual borohydrides. Rather, we find that the decomposition of LiZn2(BH4)5 is divided into a weakly exothermic step [LiZn2(BH4)5→ 2Zn+15LiBH4+25Li2B12H12+365H 2] and three strong endothermic steps (12LiBH4→ 10LiH+Li2B12H12+13H2; Zn+LiH→LiZn+12H2; 2Zn+Li2B12H 12→2LiZn+12B+6H2). DFT-calculated ΔHZPET=0K values for the first three LiZn2(BH4)5 decomposition steps are -19, +37, +74 kJ/(mol H2), respectively. The behavior of LiZn2(BH4)5 shows that mixed-metal borohydrides formed by mixing borohydrides of high and low thermodynamics stabilities do not necessarily have an intermediate decomposition tendency. Our results suggest the correct strategy to find intermediate decomposition in mixed-metal borohydrides is to search for stable mixed-metal products such as ternary metal borides.

Original languageEnglish (US)
Article number024119
JournalPhysical Review B - Condensed Matter and Materials Physics
Issue number2
StatePublished - Jul 29 2013

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics


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