First-principles calculated decomposition pathways for LiBH4 nanoclusters

Huang, Zhi -Quan; Chen, Wei -Chih; Chuang, Feng -Chuan; Majzoub, Eric H.; Ozolins, Vidvuds

doi:10.1038/srep26056

Title: First-principles calculated decomposition pathways for LiBH₄ nanoclusters

Journal Article · Wed May 18 00:00:00 EDT 2016 · Scientific Reports

DOI:https://doi.org/10.1038/srep26056· OSTI ID:1283014

Huang, Zhi -Quan ^[1]; Chen, Wei -Chih ^[1]; Chuang, Feng -Chuan ^[1]; Majzoub, Eric H. ^[2]; Ozolins, Vidvuds ^[3]

National Sun Yat-Sen Univ., Kaohsiung (Taiwan). Dept. of Physics
Univ. of Missouri-St. Louis, St. Louis, MO (United States). Center for Nanoscience and Dept. of Physics and Astronomy
Univ. of California Los Angeles, Los Angeles, CA (United States). Dept. of Materials Science and Engineering

Here, we analyze thermodynamic stability and decomposition pathways of LiBH₄ nanoclusters using grand-canonical free-energy minimization based on total energies and vibrational frequencies obtained from density-functional theory (DFT) calculations. We consider (LiBH₄)_n nanoclusters with n = 2 to 12 as reactants, while the possible products include (Li)_n, (B)_n, (LiB)_n, (LiH)_n, and Li₂B_nH_n; off-stoichiometric LinBnHm (m ≤ 4n) clusters were considered for n = 2, 3, and 6. Cluster ground-state configurations have been predicted using prototype electrostatic ground-state (PEGS) and genetic algorithm (GA) based structural optimizations. Free-energy calculations show hydrogen release pathways markedly differ from those in bulk LiBH₄. While experiments have found that the bulk material decomposes into LiH and B, with Li₂B₁₂H₁₂ as a kinetically inhibited intermediate phase, (LiBH₄)_n nanoclusters with n ≤ 12 are predicted to decompose into mixed Li_nB_n clusters via a series of intermediate clusters of Li_nB_nH_m (m ≤ 4n). The calculated pressure-composition isotherms and temperature-pressure isobars exhibit sloping plateaus due to finite size effects on reaction thermodynamics. Generally, decomposition temperatures of free-standing clusters are found to increase with decreasing cluster size due to thermodynamic destabilization of reaction products.

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Research Organization:: National Sun Yat-Sen Univ., Kaohsiung (Taiwan)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-07ER46433; AC02-05CH11231

OSTI ID:: 1283014

Journal Information:: Scientific Reports, Vol. 6; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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Title: First-principles calculated decomposition pathways for LiBH₄ nanoclusters