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LiSc(BH_4)_4 as a Hydrogen Storage Material: Multinuclear High-Resolution Solid-State NMR and First-Principles Density Functional Theory Studies

Kim, Chul and Hwang, Son-Jong and Bowman, Robert C., Jr. and Reiter, Joseph W. and Zan, Jason A. and Kulleck, James G. and Kabbour, Houria and Majzoub, E. H. and Ozolins, V. (2009) LiSc(BH_4)_4 as a Hydrogen Storage Material: Multinuclear High-Resolution Solid-State NMR and First-Principles Density Functional Theory Studies. Journal of Physical Chemistry C, 113 (22). pp. 9956-9968. ISSN 1932-7447.

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A lithium salt of anionic scandium tetraborohydride complex, LiSc(BH_4)_4, was studied both experimentally and theoretically as a potential hydrogen storage medium. Ball milling mixtures of LiBH_4 and ScCl_3 produced LiCl and a unique crystalline hydride, which has been unequivocally identified via multinuclear solid-state nuclear magnetic resonance (NMR) to be LiSc(BH_4)_4. Under the present reaction conditions, there was no evidence for the formation of binary Sc(BH_4)_3. These observations are in agreement with our first-principles calculations of the relative stabilities of these phases. A tetragonal structure in space group I (#82) is predicted to be the lowest energy state for LiSc(BH_4)_4, which does not correspond to structures obtained to date on the crystalline ternary borohydride phases made by ball milling. Perhaps reaction conditions are resulting in formation of other polymorphs, which should be investigated in future studies via neutron scattering on deuterides. Hydrogen desorption while heating these Li−Sc−B−H materials up to 400 °C yielded only amorphous phases (besides the virtually unchanged LiCl) that were determined by NMR to be primarily ScB_2 and [B_(12)H_(12)]^(−2) anion containing (e.g., Li_2B_(12)H_(12)) along with residual LiBH_4. Reaction of a desorbed LiSc(BH_4)_4 + 4LiCl mixture (from 4LiBH_4/ScCl_3 sample) with hydrogen gas at 70 bar resulted only in an increase in the contents of Li_2B_(12)H_(12) and LiBH_4. Full reversibility to reform the LiSc(BH_4)_4 was not found. Overall, the Li−Sc−B−H system is not a favorable candidate for hydrogen storage applications.

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Hwang, Son-Jong0000-0002-3210-466X
Bowman, Robert C., Jr.0000-0002-2114-1713
Additional Information:© 2009 American Chemical Society. Received: February 8, 2009; Revised Manuscript Received: April 14, 2009. Publication Date (Web): May 7, 2009. We thank Dr. Channing Ahn for his contributions and support. This research was partially performed at the Jet Propulsion Laboratory, which is operated by the California Institute of Technology under contract with the NASA. This work was partially supported by DOE through Award Nos. DE-AI-01-05EE11105 and DE-FC36-05GO15065. The NMR facility at Caltech was supported by the National Science Foundation (NSF) under Grant No. 9724240 and partially supported by the MRSEC Program of the NSF under Award No. DMR-0520565. Research at UCLA was supported by the U.S. Department of Energy under grant No. DE-FG02-07ER46433 and by the DOE INCITE program. Research at UMSL was funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, in the Hydrogen, Fuel Cells & Infrastructure Technologies Program under Contract No. DE-AC04-94AL8500.
Funding AgencyGrant Number
Department of Energy (DOE)DE-AI-01-05EE11105
Department of Energy (DOE)DE-FC36-05GO15065
Department of Energy (DOE)DE-FG02-07ER46433
Department of Energy (DOE)DE-AC04-94AL85000
Issue or Number:22
Record Number:CaltechAUTHORS:20090901-151955623
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:15539
Deposited By: George Porter
Deposited On:09 Sep 2009 18:36
Last Modified:03 Oct 2019 00:59

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