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Understanding and Mitigating the Effects of Stable Dodecahydro- closo -dodecaborate Intermediates on Hydrogen-Storage Reactions

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4];  [1]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States); Univ. of California, Santa Cruz, CA (United States)
  3. Univ. of California, Santa Cruz, CA (United States)
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
+ Show Author Affiliations
Alkali metal borohydrides can reversibly store hydrogen; however, the materials display poor cyclability, often times linked to 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.
Research Organization:
Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1338335
Report Number(s):
SAND--2016-10142J; 648158
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 45 Vol. 120; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (6)

A fleeting glimpse of the dual roles of SiB 4 in promoting the hydrogen storage performance of LiBH 4 journal January 2019
Fe 3 O 4 nanoclusters highly dispersed on a porous graphene support as an additive for improving the hydrogen storage properties of LiBH 4 journal January 2018
Molten metal closo -borate solvates journal January 2019
Potassium octahydridotriborate: diverse polymorphism in a potential hydrogen storage material and potassium ion conductor journal January 2019
First-Principles Investigation of the Mechanical and Thermodynamic Properties of the Metal-Borohydrides as Electrolytes for Solid-State Batteries journal January 2019
Direct Rehydrogenation of LiBH4 from H-Deficient Li2B12H12−x journal March 2018

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