Hydrogenation properties of lithium and sodium hydride – closo -borate, [B 10 H 10 ] 2− and [B 12 H 12 ] 2− , composites

Jensen, Steffen R. H.; Paskevicius, Mark; Hansen, Bjarne R. S.; Jakobsen, Anders S.; Møller, Kasper T.; White, James L.; Allendorf, Mark D.; Stavila, Vitalie; Skibsted, Jørgen; Jensen, Torben R.

doi:10.1039/C7CP07776A

Title: Hydrogenation properties of lithium and sodium hydride – closo -borate, [B ₁₀ H ₁₀ ] ²⁻ and [B ₁₂ H ₁₂ ] ²⁻ , composites

Journal Article · Mon Jan 01 00:00:00 EST 2018 · Physical Chemistry Chemical Physics. PCCP (Print)

DOI:https://doi.org/10.1039/C7CP07776A· OSTI ID:1470579

Jensen, Steffen R. H. ^[1];

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Center for Materials Crystallography, Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark
Chemistry, Combustion, and Materials Center, Sandia National Laboratories, Livermore, USA
Department of Chemistry and Interdisciplinary Nanoscience Center (iNANO), Aarhus University, 8000 Aarhus C, Denmark

The hydrogen absorption properties of metal closo-borate metal hydride composites, M₂B₁₀H₁₀– 8MH and M₂B₁₂H₁₂–10MH, M = Li or Na, are studied under high hydrogen pressures to understand the formation mechanism of metal borohydrides. The hydrogen storage properties of the composites have been investigated by in-situ synchrotron radiation powder X-ray diffraction at p(H₂) = 400 bar and by ex-situ hydrogen absorption measurements at p(H₂) = 526 to 998 bar. The in-situ experiments reveal the formation of crystalline intermediates before metal borohydrides (MBH₄) are formed. The M₂B₁₂H₁₂–10MH (M = Li and Na) systems show no formation of the metal borohydride at T = 400 °C and p(H₂) = 537 to 970 bar. ¹¹B MAS NMR of the M₂B₁₀H₁₀– 8MH composites reveal that the molar ratio of LiBH₄ or NaBH₄ and the remaining B species is 1:0.63 and 1:0.21, respectively. Solution and solid-state ¹¹B NMR spectra reveal new intermediates with a B:H ratio close to 1:1. Our results indicate that the M₂B₁₀H₁₀ (M = Li, Na) salts display a higher reactivity towards hydrogen in the presence of metal hydrides compared to the corresponding [B₁₂H₁₂]^2- compounds, which represents an important step towards understanding the factors that determine the stability and reversibility of high hydrogen capacity metal borohydrides for hydrogen storage.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office

Grant/Contract Number:: AC04-94AL85000; NA0003525

OSTI ID:: 1470579

Alternate ID(s):: OSTI ID: 1429663; OSTI ID: 1440264; OSTI ID: 1444088

Report Number(s):: SAND-2017-11502J; SAND-2018-6006J; PPCPFQ

Journal Information:: Physical Chemistry Chemical Physics. PCCP (Print), Journal Name: Physical Chemistry Chemical Physics. PCCP (Print) Vol. 20 Journal Issue: 23; ISSN 1463-9076

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cited by: 13 works

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