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Title: 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 Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1338335
Report Number(s):
SAND-2016-10142J; 648158
Journal Information:
Journal of Physical Chemistry. C, Vol. 120, Issue 45; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

References (47)

Complex Hydrides for Hydrogen Storage journal October 2007
Experimental studies on intermediate compound of LiBH4 journal July 2006
NMR Confirmation for Formation of [B 12 H 12 ] 2- Complexes during Hydrogen Desorption from Metal Borohydrides journal March 2008
Dehydriding and rehydriding processes of well-crystallized Mg(BH4)2 accompanying with formation of intermediate compounds journal April 2008
Formation of an intermediate compound with a B 12 H 12 cluster: experimental and theoretical studies on magnesium borohydride Mg(BH 4 ) 2 journal April 2009
Magnesium borohydride as a hydrogen storage material: Properties and dehydrogenation pathway of unsolvated Mg(BH4)2 journal January 2009
Can Na2[B12H12] be a decomposition product of NaBH4? journal January 2010
Role of Li 2 B 12 H 12 for the Formation and Decomposition of LiBH 4 journal May 2010
Experimental Evidence of Na 2 [B 12 H 12 ] and Na Formation in the Desorption Pathway of the 2NaBH 4 + MgH 2 System journal August 2011
Experimental Evidence of Ca[B 12 H 12 ] Formation During Decomposition of a Ca(BH 4 ) 2 + MgH 2 Based Reactive Hydride Composite journal August 2011
Formation Process of [B12H12]2− from [BH4]− during the Dehydrogenation Reaction of Mg(BH4)2 journal January 2011
Formation of Intermediate Compound Li 2 B 12 H 12 during the Dehydrogenation Process of the LiBH 4 –MgH 2 System journal September 2011
Investigation of the Dehydrogenation Reaction Pathway of Ca(BH 4 ) 2 and Reversibility of Intermediate Phases journal February 2012
Thermal Stability of Li 2 B 12 H 12 and its Role in the Decomposition of LiBH 4 journal April 2013
Dehydrogenation Reaction Pathway of the LiBH 4 –MgH 2 Composite under Various Pressure Conditions journal April 2015
The role of MgB 12 H 12 in the hydrogen desorption process of Mg(BH 4 ) 2 journal January 2015
The electronic structure of an icosahedron of boron atoms
  • Longuet-Higgins, Hugh Christopher; Roberts, M. De V.
  • Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 230, Issue 1180, p. 110-119 https://doi.org/10.1098/rspa.1955.0115
journal June 1955
THE ISOLATION OF THE ICOSAHEDRAL B 12 H 12 -2 ION journal June 1960
Reversible Storage of Hydrogen in Destabilized LiBH 4 journal March 2005
Destabilizing LiBH 4 with a Metal (M = Mg, Al, Ti, V, Cr, or Sc) or Metal Hydride (MH 2 = MgH 2 , TiH 2 , or CaH 2 ) journal December 2007
Hydrogen Sorption Behavior of the ScH 2 −LiBH 4 System: Experimental Assesment of Chemical Destabilization Effects journal May 2008
Hydrogen storage in destabilized borohydride materials journal October 2010
NbF5 additive improves hydrogen release from magnesium borohydride journal December 2012
Improved hydrogen storage reversibility of LiBH4 destabilized by Y(BH4)3 and YH3 journal December 2012
Beneficial effects of stoichiometry and nanostructure for a LiBH 4 –MgH 2 hydrogen storage system journal January 2014
First-Principles Prediction of Thermodynamically Reversible Hydrogen Storage Reactions in the Li-Mg-Ca-B-H System journal January 2009
Probing the structure, stability and hydrogen storage properties of calcium dodecahydro-closo-dodecaborate journal May 2010
Is Y2(B12H12)3 the main intermediate in the decomposition process of Y(BH4)3? journal January 2013
Intermediate Phases during Decomposition of Metal Borohydrides, M(BH 4 ) n (M = Na, Mg, Y) journal November 2014
Thermal Decomposition of Anhydrous Alkali Metal Dodecaborates M2B12H12 (M = Li, Na, K) journal November 2015
In situ characterization of the decomposition behavior of Mg(BH 4 ) 2 by X-ray Raman scattering spectroscopy journal January 2016
Kinetics studies of the reversible partial decomposition reaction in Mg(BH4)2 journal June 2016
Facile synthesis of anhydrous alkaline earth metal dodecaborates MB 12 H 12 (M = Mg, Ca) from M(BH 4 ) 2 journal January 2015
Die Dodekahydro-closo-Dodekaborate M2[B12H12] der schweren Alkalimetalle (M+ = K+, Rb+, NH4+, Cs+) und ihre formalen Iodid-Addukte M3I[B12H12] (≡ MI · M2[B12H12]) journal July 2003
Crystal Structure of Li 2 B 12 H 12 : a Possible Intermediate Species in the Decomposition of LiBH 4 journal November 2008
Role of Cation Size on the Structural Behavior of the Alkali-Metal Dodecahydro- closo -Dodecaborates journal June 2009
Mechanochemical synthesis of hydrogen storage materials journal January 2013
Dynamical Perturbations of Tetrahydroborate Anions in LiBH 4 due to Nanoconfinement in Controlled-Pore Carbon Scaffolds journal August 2013
Reorientational Dynamics of NaBH 4 and KBH 4 journal May 2010
Inelastic neutron scattering spectra of NaBH4 and KBH4: reproduction of anion mode shifts via periodic DFT journal February 2004
Hydrogen dynamics in heavy alkali metal hydrides obtained through inelastic neutron scattering journal August 2004
Alkali and alkaline-earth metal dodecahydro-closo-dodecaborates: Probing structural variations via neutron vibrational spectroscopy journal September 2011
Structural Behavior of Li 2 B 10 H 10 journal March 2015
The structure of monoclinic Na 2 B 10 H 10 : a combined diffraction, spectroscopy, and theoretical approach journal January 2015
Crystal structures and properties of divalent transition metal decahydro-closo-decaborate hydrates [M(H2O)6][B10H10] · 2H2O (M = Mn, Fe, Co, Ni, Zn) journal January 2013
Structural and spectroscopic characterization of potassium fluoroborohydrides journal January 2013
New Insights into the Thermodynamic Behavior of 2LiBH 4 –MgH 2 Composite for Hydrogen Storage journal June 2015

Cited By (6)

First-Principles Investigation of the Mechanical and Thermodynamic Properties of the Metal-Borohydrides as Electrolytes for Solid-State Batteries journal January 2019
Potassium octahydridotriborate: diverse polymorphism in a potential hydrogen storage material and potassium ion conductor journal January 2019
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
Direct Rehydrogenation of LiBH4 from H-Deficient Li2B12H12−x journal March 2018
Molten metal closo -borate solvates journal January 2019

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