First‐Principles Determination of Multicomponent Hydride Phase Diagrams: Application to the Li‐Mg‐N‐H System

Akbarzadeh, Alireza; Ozoliņš, Vidvuds; Wolverton, Christopher

doi:10.1002/adma.200700843

Cited by 232 publications

(254 citation statements)

References 34 publications

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“…The GCLP method is capable of delineating all thermodynamically-realistic reactions occuring within a prescribed composition space. 113,126,132 As initially constructed, the method relies upon DFT-calculated free energies, and focused on reactions within the Li-N-Mg-H composition space. 132 By predicting thermodynamicallyrealistic reaction pathways, this approach eliminates the need to ''guess'' at what reactions could occur.…”

Section: Methods For Thermodynamic Assessmentmentioning

confidence: 99%

“…113,126,132 As initially constructed, the method relies upon DFT-calculated free energies, and focused on reactions within the Li-N-Mg-H composition space. 132 By predicting thermodynamicallyrealistic reaction pathways, this approach eliminates the need to ''guess'' at what reactions could occur. 99,113,133 Despite the advantages afforded by first-principles computation, its utility for predicting the properties of new or hypothetical materials-i.e., compounds which have yet to be synthesized, or for which the crystal structure is not known-remains a key challenge.…”

Section: Methods For Thermodynamic Assessmentmentioning

confidence: 99%

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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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Section: Methods For Thermodynamic Assessmentmentioning

confidence: 99%

Section: Methods For Thermodynamic Assessmentmentioning

confidence: 99%

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

et al. 2010

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“…For further details on GCLP, we refer the reader to Ref. [ 22 ]. The following phases are included in this study: in the "convex-hull" plot in Fig.…”

Section: Methodsmentioning

confidence: 99%

“…By contrast, for the DFT calculations in this work, the crystal structure information is currently not available. To solve this problem, we have used a recently developed crystal structure prediction method, known as the prototype electrostatic ground state (PEGS) approach, which has been successfully shown to predict low energy crystal structure for ionically-bonded systems such as alanates, 22 borohydrides 54 and imides. 55 In addition, this approach has also been used to predict crystal structures for double cation borohydrides, i.e., M 1 M 2 (BH 4 ) x (where M 1 and M 2 represent different metal cations) 56,57,58 In the present work, for the first time, we use this approach to predict crystal structure of a double anion system, i.e., containing (BH 4 ) -and (NH 2 ) -units.…”

Section: Methodsmentioning

confidence: 99%

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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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Energy Storage: Hydrogen

Kim

2013

Computational Approaches to Energy Materials

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First‐Principles Determination of Multicomponent Hydride Phase Diagrams: Application to the Li‐Mg‐N‐H System

Cited by 232 publications

References 34 publications

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

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

Energy Storage: Hydrogen

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