The influence of LiH and TiH2 on hydrogen storage in MgB2 II. XPS study of surface and near-surface phenomena

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

doi:10.1016/j.ijhydene.2021.09.163

The influence of LiH and TiH₂ on hydrogen storage in MgB₂ II. XPS study of surface and near-surface phenomena

Journal Article · Tue Nov 02 00:00:00 EDT 2021 · International Journal of Hydrogen Energy

DOI:https://doi.org/10.1016/j.ijhydene.2021.09.163· OSTI ID:1860733

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

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, 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)

We report that Mg(BH₄)₂ is a promising solid-state hydrogen storage material, releasing 14.9 wt% hydrogen upon conversion to MgB₂. The rehydrogenation of MgB₂ is particularly challenging, requiring prolonged exposure to high pressures of hydrogen at high temperature. Here we report an XPS study probing the influence of LiH and TiH₂ on the hydrogen storage properties of MgB₂ in the surface and near-surface regions, as a complementary investigation to a preceding study of the bulk properties. Surface and near-surface properties are important considerations for nanoscale and bulk hydrogen storage materials. If there are reactions occurring at the surface that modify the chemical composition in the near-surface region, species diffusion can alter the chemical composition even deep into the bulk of the material. For LiH/MgB₂, metastable LiH–B and LiH–Mg species are produced that are more reactive than Bulk MgB₂. With prolonged glovebox storage, the LiH/MgB₂ material shows increased reactivity towards O and C and enriched levels of Li and B in the near-surface region. In addition, Li induces the growth of Li₂CO₃ in the surface and near surface regions. Exposing LiH/MgB₂ to hydrogen at 700 bar and 280 °C for 24 h produces borohydride at a temperature 100 °C below the threshold for bulk MgB₂ hydrogenation. In a specifically surface process with macroscopic implications, the hydrogenation conditions also cause Li₂CO₃ to react with boron hydroxide in the sample to form a Li-deficient glassy lithium borate melt at the interfaces of the particles, bonding them together. Subsequent heating to 380 °C dehydrogenates the borohydride and eliminates the Li-deficient glassy lithium borate. The LiH/MgB₂ material is not reversible because desorption does not lead back to LiH/MgB₂, but rather to elemental B and Mg metal in the near-surface region. In contrast to LiH, TiH₂ does not react with MgB₂, despite the favorable thermodynamics for destabilization via TiB₂ formation. Furthermore, high pressure hydrogenation yields only unreacted TiH₂ and MgB₂ in the surface and near-surface regions. Thus, added TiH₂ provides no benefit to MgB₂ hydrogenation, in agreement with the findings of the preceding bulk study.

View Accepted Manuscript (DOE)

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

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

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

OSTI ID:: 1860733

Report Number(s):: LLNL-JRNL-823826; 1036578

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

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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