Publications

White, James L.; Stavila, Vitalie S.; Allendorf, Mark D.

Abstract not provided.

Journal of Physical Chemistry C

Vajo, John J.; Tan, Hongjin; Ahn, Channing C.; Addison, Dan; Hwang, Son J.; White, James L.; Wang, Timothy C.; Stavila, Vitalie S.; Graetz, Jason

Use of electrolytes, in the form of LiBH4/KBH4 and LiI/KI/CsI eutectics, is shown to significantly improve (by more than a factor of 10) both the dehydrogenation and full rehydrogenation of the MgH2/Sn destabilized hydride system and the hydrogenation of MgB2 to Mg(BH4)2. The improvement revealed that interparticle transport of atoms heavier than hydrogen can be an important rate-limiting step during hydrogen cycling in hydrogen storage materials consisting of multiple phases in powder form. Electrolytes enable solubilizing heavy ions into a liquid environment and thereby facilitate the reaction over full surface areas of interacting particles. The examples presented suggest that use of electrolytes in the form of eutectics, ionic liquids, or solvents containing dissolved salts may be generally applicable for increasing reaction rates in complex and destabilized hydride materials.

White, James L.; Rowberg, Andrew J.; Wan, Liwen F.; Kang, ShinYoung K.; Ogitsu, Tadashi O.; Kolasinski, Robert K.; Whaley, Josh A.; Wang, Timothy C.; Baker, Alexander A.; Lee, Jonathan R.; Liu, Yi-Sheng L.; Guo, Jinghua G.; Stavila, Vitalie S.; Prendergast, David P.; Bluhm, Hendrik B.; Allendorf, Mark D.; Wood, Brandon C.; El Gabaly Marquez, Farid E.

Abstract not provided.

White, James L.; El Gabaly Marquez, Farid E.

Abstract not provided.

White, James L.

Abstract not provided.

Proposed for publication

White, James L.; Rowberg, Andrew J.; Wan, Liwen F.; Kang, ShinYoung K.; Ogitsu, Tadashi O.; Kolasinski, Robert K.; Whaley, Josh A.; Baker, Alexander A.; Lee, Jonathan R.; Liu, Yi-Sheng L.; Trotochaud, Lena T.; Guo, Jinghua G.; Stavila, Vitalie S.; Prendergast, David P.; Bluhm, Hendrik B.; Allendorf, Mark D.; Wood, Brandon C.; El Gabaly Marquez, Farid E.

Abstract not provided.

White, James L.

Abstract not provided.

Kolasinski, Robert K.; Whaley, Josh A.; El Gabaly Marquez, Farid E.; Klebanoff, Leonard E.; Stavila, Vitalie S.; White, James L.; Allendorf, Mark D.

Abstract not provided.

White, James L.; Ogitsu, Tadashi O.; Kolasinski, Robert K.; Kang, ShinYoung K.; Stavila, Vitalie S.; Allendorf, Mark D.; Wood, Brandon C.; El Gabaly Marquez, Farid E.

Abstract not provided.

Allendorf, Mark D.; Stavila, Vitalie S.; Klebanoff, Leonard E.; Kolasinski, Robert K.; El Gabaly Marquez, Farid E.; Zhou, Xiaowang Z.; White, James L.

The Sandia HyMARC team continued its development of new synthetic, modeling, and diagnostic tools that are providing new insights into all major classes of storage materials, ranging from relatively simple systems such as PdHx and MgH2, to exceptionally complex ones, such as the metal borohydrides, as well as materials thought to be very well-understood, such as Ti-doped NaAlH4. This unprecedented suite of capabilities, capable of probing all relevant length scales within storage materials, is already having a significant impact, as they are now being used by both Seedling projects and collaborators at other laboratories within HyMARC. We expect this impact to grow as new Seedling projects begin and through collaborations with other scientists outside HyMARC. In the coming year, Sandia efforts will focus on the highest impact problems, in coordination with the other HyMARC National Laboratory partners, to provide the foundational science necessary to accelerate the discovery of new hydrogen storage materials.

Edgington, Jane E.; White, James L.; Benin, Annabelle L.; Stavila, Vitalie S.; Allendorf, Mark D.

Abstract not provided.

White, James L.; Stavila, Vitalie S.; Wood, Brandon C.; Klebanoff, Leonard E.; Majzoub, Eric H.; Allendorf, Mark D.

Abstract not provided.

Stavila, Vitalie S.; White, James L.; Kolasinski, Robert K.; Klebanoff, Leonard E.; El Gabaly Marquez, Farid E.; Zhou, Xiaowang Z.; Heo, Tae W.; Lee, Jon L.; Wood, Brandon C.; Allendorf, Mark D.

Abstract not provided.

Kolasinski, Robert K.; Whaley, Josh A.; Stavila, Vitalie S.; White, James L.; El Gabaly Marquez, Farid E.; Allendorf, Mark D.

Abstract not provided.

Journal of Physical Chemistry C

White, James L.; Newhouse, Rebecca J.; Zhang, Jin Z.; Udovic, Terrence J.; Stavila, Vitalie S.

Alkali metal borohydrides can reversibly store hydrogen; however, the materials display poor cyclability, oftentimes linked to the occurrence of stable closo-polyborate intermediate species. In an effort to understand the role of such intermediates on the hydrogen storage properties of metal borohydrides, several alkali metal dodecahydro-closo-dodecaborate salts were isolated in anhydrous form and characterized by diffraction and spectroscopic techniques. Mixtures of Li2B12H12, Na2B12H12, and K2B12H12 with the corresponding alkali metal hydrides were subjected to hydrogenation conditions known to favor partial or full reversibility in metal borohydrides. The stoichiometric mixtures of MH and M2B12H12 salts form the corresponding metal borohydrides MBH4 (M = Li, Na, K) in almost quantitative yield at 100 MPa H2 and 500°C. In addition, stoichiometric mixtures of Li2B12H12 and MgH2 were found to form MgB2 at 500°C and above upon desorption in vacuum. The two destabilization strategies outlined above suggest that metal polyhydro-closo-polyborate species can be converted into the corresponding metal borohydrides or borides, albeit under rather harsh conditions of hydrogen pressure and temperature. (Chemical Equation Presented).

White, James L.; El Gabaly Marquez, Farid E.; Kolasinski, Robert K.; Wood, Brandon C.; Klebanoff, Leonard E.; Allendorf, Mark D.; Stavila, Vitalie S.

Abstract not provided.

Stavila, Vitalie S.; Klebanoff, Leonard E.; Kolasinski, Robert K.; El Gabaly Marquez, Farid E.; Zhou, Xiaowang Z.; White, James L.; Zimmerman, Jonathan A.; Allendorf, Mark D.

Abstract not provided.

White, James L.; Stavila, Vitalie S.; Allendorf, Mark D.; Woods, Brandon C.; Sugar, Joshua D.; El Gabaly Marquez, Farid E.; Kolasinski, Robert K.; Klebanoff, Leonard E.; Zhou, Xiaowang Z.

Abstract not provided.

Stavila, Vitalie S.; Klebanoff, Leonard E.; Kolasinski, Robert K.; El Gabaly Marquez, Farid E.; Zhou, Xiaowang Z.; White, James L.; Allendorf, Mark D.

Abstract not provided.

Physical Chemistry Chemical Physics

Dimitrievska, Mirjana; White, James L.; Zhou, Wei; Stavila, Vitalie S.; Klebanoff, Leonard E.; Udovic, Terrence J.

The structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (α, β, γ, and δ phases) were investigated with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20-80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80-120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120-200 meV) correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. This is explained by the differences in the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. These results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.