Nanoscale Mg–B via Surfactant Ball Milling of MgB2: Morphology, Composition, and Improved Hydrogen Storage Properties

Liu, Y. -S.; Ray, K. G.; Jørgensen, M.; Mattox, T. M.; Cowgill, D. F.; Eshelman, H. V.; Sawvel, A. M.; Snider, J. L.; York, W.; Wijeratne, P.; Pham, A. L.; Gunda, H.; Li, S.; Heo, T. W.; Kang, S.; Jensen, T. R.; Stavila, V.; Wood, B. C.; Klebanoff, L. E.

doi:10.1021/acs.jpcc.0c05142

Nanoscale Mg–B via Surfactant Ball Milling of MgB₂: Morphology, Composition, and Improved Hydrogen Storage Properties

Journal Article · Fri Sep 04 00:00:00 EDT 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c05142· OSTI ID:1670751

^[1]; Ray, K. G. ^[2]; Jørgensen, M. ^[3]; Mattox, T. M. ^[4]; Cowgill, D. F. ^[5]; Eshelman, H. V. ^[2]; ^[2]; Snider, J. L. ^[5]; York, W. ^[5]; Wijeratne, P. ^[5]; Pham, A. L. ^[4]; Gunda, H. ^[6]; ^[2]; ^[2]; Kang, S. ^[2]; ^[3]; ^[5]; ^[2]; ^[5]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Aarhus Univ. (Denmark)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Indian Inst. of Technology (IIT), Gandhinagar (India)

Metal borides have attracted the attention of researchers due to their useful physical properties and unique ability to form high hydrogen-capacity metal borohydrides. We demonstrate improved hydrogen storage properties of a nanoscale Mg–B material made by surfactant ball milling MgB₂ in a mixture of heptane, oleic acid, and oleylamine. Transmission electron microscopy data show that Mg–B nanoplatelets are produced with sizes ranging from 5 to 50 nm, which agglomerate upon ethanol washing to produce an agglomerated nanoscale Mg–B material of micron-sized particles with some surfactant still remaining. X-ray diffraction measurements reveal a two-component material where 32% of the solid is a strained crystalline solid maintaining the hexagonal structure with the remainder being amorphous. Fourier transform infrared shows that the oleate binds in a “bridge-bonding” fashion preferentially to magnesium rather than boron, which is confirmed by density functional theory calculations. The Mg–B nanoscale material is deficient in boron relative to bulk MgB₂ with a Mg–B ratio of ~1:0.75. The nanoscale MgB_0.75 material has a disrupted B–B ring network as indicated by X-ray absorption measurements. Hydrogenation experiments at 700 bar and 280 °C show that it partially hydrogenates at temperatures 100 °C below the threshold for bulk MgB₂ hydrogenation. In addition, upon heating to 200 °C, the H–H bond-breaking ability increases ~10-fold according to hydrogen–deuterium exchange experiments due to desorption of oleate at the surface. This behavior would make the nanoscale Mg–B material useful as an additive where rapid H–H bond breaking is needed.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1670751

Alternate ID(s):: OSTI ID: 1811217

Report Number(s):: SAND--2020-4788J; 685921

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 39 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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