The influence of LiH and TiH2 on hydrogen storage in MgB2 I: Promotion of bulk hydrogenation at reduced temperature

Snider, J. L.; Liu, Y. -S.; Sawvel, A. M.; Wan, L. F.; Stavila, V.; Mattox, T. M.; Wijeratne, P.; Allendorf, M. D.; Wood, B. C.; Klebanoff, L. E.

doi:10.1016/j.ijhydene.2021.09.169

Title: The influence of LiH and TiH₂ on hydrogen storage in MgB₂ I: Promotion of bulk hydrogenation at reduced temperature

Journal Article · Wed Oct 27 00:00:00 EDT 2021 · International Journal of Hydrogen Energy

DOI:https://doi.org/10.1016/j.ijhydene.2021.09.169· OSTI ID:1860734

Snider, J. L. ^[1]; Liu, Y. -S. ^[2]; Sawvel, A. M. ^[3]; Wan, L. F. ^[3]; Stavila, V. ^[1]; Mattox, T. M. ^[4]; Wijeratne, P. ^[1]; Allendorf, M. D. ^[1]; Wood, B. C. ^[3]; Klebanoff, L. E. ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Mg(BH₄)₂ is an attractive hydrogen storage material, owing to its high gravimetric capacity of 14.9 wt %. However, the dehydrogenated material MgB₂ is very difficult to rehydrogenate, requiring excessive pressures and temperatures. Here we report the influence of LiH and TiH₂ on hydrogen storage reactions involving Bulk MgB₂ using XRD, XAS, FTIR and NMR. In ball-milled mixtures of LiH/MgB₂, the LiH loses crystallinity but remains undissociated, forming a weakly bound complex with MgB₂. The weak interactions produce minor variations in the local electronic structure at B and Mg, but do not markedly affect the underlying MgB₂ hexagonal crystal structure. No evidence is found for a mixed-metal boride Mg_1-xLi_xB₂ in the as-prepared LiH/MgB₂ materials. The presence of LiH dramatically improves the hydrogenation of MgB₂ at 700 bar, forming borohydride 100 °C below the minimum hydrogenation temperature of pure MgB₂ and without the formation of undesirable intermediates such as [B₃H₈]^-, [B₁₀H₁₀]^2- or [B₁₂H₁₂]^2-. Evidence is reported for a mixed-metal borohydride of the type Mg_(3-x)/2Li_x(BH₄)₃ produced by the hydrogenation. Subsequent desorption is also improved compared to pure Mg(BH₄)₂ and LiBH₄, showing single-step hydrogen release up to ~8 wt% by 380 °C, whereas Mg(BH₄)₂ and LiBH₄ still retain significant amounts of hydrogen at this temperature. The material produced by desorption contains both MgB₂ and Mg metal, revealing the original LiH/MgB₂ system is not fully reversible. In contrast to LiH, TiH₂ is essentially inert when ball-milled with MgB₂, and high-pressure hydrogenation leaves only unreacted TiH₂ and MgB₂. Thus, added TiH₂ provides no benefit to MgB₂ hydrogenation.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

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

Grant/Contract Number:: AC52-07NA27344; AC04-94AL85000; NA0003525; AC02-05CH11231

OSTI ID:: 1860734

Report Number(s):: LLNL-JRNL-823824; 1036577

Journal Information:: International Journal of Hydrogen Energy, Vol. 47, Issue 1; ISSN 0360-3199

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: The influence of LiH and TiH₂ on hydrogen storage in MgB₂ I: Promotion of bulk hydrogenation at reduced temperature