First-Principles Prediction of Thermodynamically Reversible Hydrogen Storage Reactions in the Li-Mg-Ca-B-H System

Ozoliņš, Vidvuds; Majzoub, Eric H.; Wolverton, Christopher

doi:10.1021/ja8066429

Cited by 264 publications

(402 citation statements)

References 55 publications

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“…In fact, in order to promote reaction (15) and overcome the kinetic barrier, the temperature has to be signifi-cantly increased. So, even if some uncertainties are related to the thermodynamic stability of Li 2 B 12 H 12 , because assessed para-meters are based only on ab-initio calculations [45], it appears that its formation, even if thermodynamically favoured, must be kinetically hindered.…”

Section: Consistency Of Results and Discussionmentioning

confidence: 99%

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A thermodynamic assessment of LiBH4

Kharbachi

Pinatel

Nuta

et al. 2012

Calphad

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a b s t r a c t Thermodynamic data of the LiBH 4 compound are reviewed and critically assessed. On the basis of literature data of heat capacity, heat of formation, temperature and enthalpy of phase transitions, a CALPHAD optimized Gibbs energy function is derived for the condensed phases i.e. orthorhombic and hexagonal solid phases and the liquid phase. Considering hydrogen as an ideal gas phase, the thermodynamics of decomposition reactions of LiBH 4 is calculated, showing good agreement with existing experimental data.

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Section: Consistency Of Results and Discussionmentioning

confidence: 99%

“…[45] for the following reactions at 300 K: Li 2 B 12 H 12 ¼2LiHþ12Bþ5H 2 and 12LiBH 4 ¼Li 2 B 12 H 12 þ10LiHþ13H 2 .…”

Section: Liquid Phasementioning

confidence: 99%

A thermodynamic assessment of LiBH4

Kharbachi

Pinatel

Nuta

et al. 2012

Calphad

View full text Add to dashboard Cite

show abstract

“…37,99,113,[122][123][124][125][126] This approach can vastly improve the useful throughput of experiments by narrowing the phase space of candidate materials to those exhibiting thermodynamic potential.…”

Section: Methods For Thermodynamic Assessmentmentioning

confidence: 99%

“…Although the destabilization concept dates to the 1960s, 36 37,99,122,123 and examined by experiment. 35,38,40 Another potential avenue for altering thermodynamics is via extreme reduction in particle size.…”

Section: Altering Thermodynamics: Destabilization and Nanosizingmentioning

confidence: 99%

High capacity hydrogenstorage materials: attributes for automotive applications and techniques for materials discovery

et al. 2010

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Widespread adoption of hydrogen as a vehicular fuel depends critically upon the ability to store hydrogen on-board at high volumetric and gravimetric densities, as well as on the ability to extract/insert it at sufficiently rapid rates. As current storage methods based on physical means-high-pressure gas or (cryogenic) liquefaction-are unlikely to satisfy targets for performance and cost, a global research effort focusing on the development of chemical means for storing hydrogen in condensed phases has recently emerged. At present, no known material exhibits a combination of properties that would enable high-volume automotive applications. Thus new materials with improved performance, or new approaches to the synthesis and/or processing of existing materials, are highly desirable. In this critical review we provide a practical introduction to the field of hydrogen storage materials research, with an emphasis on (i) the properties necessary for a viable storage material, (ii) the computational and experimental techniques commonly employed in determining these attributes, and (iii) the classes of materials being pursued as candidate storage compounds. Starting from the general requirements of a fuel cell vehicle, we summarize how these requirements translate into desired characteristics for the hydrogen storage material. Key amongst these are: (a) high gravimetric and volumetric hydrogen density, (b) thermodynamics that allow for reversible hydrogen uptake/release under near-ambient conditions, and (c) fast reaction kinetics. To further illustrate these attributes, the four major classes of candidate storage materials-conventional metal hydrides, chemical hydrides, complex hydrides, and sorbent systems-are introduced and their respective performance and prospects for improvement in each of these areas is discussed. Finally, we review the most valuable experimental and computational techniques for determining these attributes, highlighting how an approach that couples computational modeling with experiments can significantly accelerate the discovery of novel storage materials (155 references).

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“…14,18,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53 In these calculations, the a priori knowledge of a compound's crystal structure is typically obtained from experiments where the system has already been structurally well characterized. By contrast, for the DFT calculations in this work, the crystal structure information is currently not available.…”

Section: Methodsmentioning

confidence: 99%

Prediction of a Ca(BH4)(NH2) quaternary hydrogen storage compound from first-principles calculations

2011

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We use a combination of density functional theory (DFT) calculations, and a Monte Carlo based crystal structure prediction tool, the Prototype Electrostatic Ground State (PEGS) method, to search for new hydrogen storage compounds in the Ca based mixed amide-borohydride quaternary system. We predict the existence of a new ordered quaternary compound, CaBNH 6 , whose stoichiometry comes from a 1:1 mixture of Ca(BH 4 ) 2 and Ca(NH 2 ) 2 . Our DFT calculations show that CaBNH 6 is ~12.5 kJ/mol Ca (at T = 0 K) lower in energy than the mixture of 1/2[Ca(BH 4 ) 2 + Ca(NH 2 ) 2 ]. DFT phonon calculations of vibrational thermodynamics show that this stability of CaBNH 6 [with respect to Ca(BH 4 ) 2 and Ca(NH 2 ) 2 ] persists to finite temperatures. The predicted crystal structure contains two formula units of CaBNH 6 . We have also performed a thermodynamic analysis of hydrogen decomposition of our predicted compound using the Grand Canonical Linear Programming (GCLP) method combined with a large database of DFT energies and vibrational thermodynamics. We find that the thermodynamically preferred decomposition reaction for CaBNH 6 involves formation of BN with a low decomposition enthalpy. Though the decomposition enthalpy is low, the kinetic behavior of CaBNH 6 decomposition is not yet known. We assert that further experimental investigation of this system is warranted to verify the existence of predicted quaternary compounds in this Ca-B-N-H system, as well as to elucidate their hydrogen release reaction pathways.3

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First-Principles Prediction of Thermodynamically Reversible Hydrogen Storage Reactions in the Li-Mg-Ca-B-H System

Cited by 264 publications

References 55 publications

A thermodynamic assessment of LiBH4

A thermodynamic assessment of LiBH4

High capacity hydrogenstorage materials: attributes for automotive applications and techniques for materials discovery

Prediction of a Ca(BH4)(NH2) quaternary hydrogen storage compound from first-principles calculations

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