TY - JOUR
T1 - Reaction energetics and crystal structure of Li4 BN3 H10 from first principles
AU - Siegel, Donald J.
AU - Wolverton, C.
AU - Ozoliņš, V.
N1 - Copyright:
Copyright 2007 Elsevier B.V., All rights reserved.
PY - 2007
Y1 - 2007
N2 - Using density functional theory we examine the crystal structure and the finite-temperature thermodynamics of formation and dehydrogenation for the quaternary hydride Li4 BN3 H10. Two recent studies based on x-ray and neutron diffraction have reported three bcc crystal structures for this phase. While these structures possess identical space groups and similar lattice constants, internal coordinate differences result in bond length discrepancies as large as 0.2 Å. Geometry optimization calculations on the experimental structures reveal that the apparent discrepancies are an artifact of x-ray interactions with strong bond polarization; the relaxed structures are essentially identical. Regarding reaction energetics, the present calculations predict that the formation reaction 3 LiNH2 + LiBH4 → Li4 BN3 H10 is exothermic with enthalpy Δ HT=300 K =-11.8 kJ/ (mol f.u.), consistent with reports of spontaneous Li4 BN3 H10 formation in the literature. Calorimetry experiments have been reported for the dehydrogenation reaction, but have proven difficult to interpret. To help clarify the thermodynamics we evaluate the free energies of seventeen candidate dehydrogenation pathways over the temperature range T=0-1000 K. At temperatures where H2 release has been experimentally observed (T≈520-630 K), the favored dehydrogenation reaction is Li4 BN3 H10 → Li3 BN2 + LiNH2 +4 H2, which is weakly endothermic [Δ HT=550 K =12.8 kJ/(mol H2)]. The small calculated ΔH is consistent with the unsuccessful attempts at rehydriding reported in the literature, and suggests that the moderately high temperatures needed for H desorption result from slow kinetics.
AB - Using density functional theory we examine the crystal structure and the finite-temperature thermodynamics of formation and dehydrogenation for the quaternary hydride Li4 BN3 H10. Two recent studies based on x-ray and neutron diffraction have reported three bcc crystal structures for this phase. While these structures possess identical space groups and similar lattice constants, internal coordinate differences result in bond length discrepancies as large as 0.2 Å. Geometry optimization calculations on the experimental structures reveal that the apparent discrepancies are an artifact of x-ray interactions with strong bond polarization; the relaxed structures are essentially identical. Regarding reaction energetics, the present calculations predict that the formation reaction 3 LiNH2 + LiBH4 → Li4 BN3 H10 is exothermic with enthalpy Δ HT=300 K =-11.8 kJ/ (mol f.u.), consistent with reports of spontaneous Li4 BN3 H10 formation in the literature. Calorimetry experiments have been reported for the dehydrogenation reaction, but have proven difficult to interpret. To help clarify the thermodynamics we evaluate the free energies of seventeen candidate dehydrogenation pathways over the temperature range T=0-1000 K. At temperatures where H2 release has been experimentally observed (T≈520-630 K), the favored dehydrogenation reaction is Li4 BN3 H10 → Li3 BN2 + LiNH2 +4 H2, which is weakly endothermic [Δ HT=550 K =12.8 kJ/(mol H2)]. The small calculated ΔH is consistent with the unsuccessful attempts at rehydriding reported in the literature, and suggests that the moderately high temperatures needed for H desorption result from slow kinetics.
UR - http://www.scopus.com/inward/record.url?scp=33846301652&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33846301652&partnerID=8YFLogxK
U2 - 10.1103/PhysRevB.75.014101
DO - 10.1103/PhysRevB.75.014101
M3 - Article
AN - SCOPUS:33846301652
SN - 1098-0121
VL - 75
JO - Physical Review B - Condensed Matter and Materials Physics
JF - Physical Review B - Condensed Matter and Materials Physics
IS - 1
M1 - 014101
ER -