Complex Hydrides for Hydrogen Storage

Orimo, Shin Ichi; Nakamori, Yoshiteru; Eliseo, Jennifer R.; Züttel, A.; Jensen, Craig M.

doi:10.1021/cr0501846

Cited by 2,049 publications

(1,375 citation statements)

References 244 publications

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“…More detailed reviews of the properties of complex hydrides are available elsewhere. 44,45 Sorbents Another approach to hydrogen storage utilizes porous lightweight materials (sorbents) with high surface areas. The interaction between hydrogen and most sorbents involves molecular hydrogen (H 2 ) and can therefore be described as a (weak) physisorptive attraction.…”

Section: Complex Hydridesmentioning

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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Section: Complex Hydridesmentioning

confidence: 99%

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

et al. 2010

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“…[3][4][5] Particularly, the combination of light-weight metal hydrides and amides leads to a series of composite systems, such as, LiNH 2 /LiH, Mg(NH 2 ) 2 /LiH, Mg(NH 2 ) 2 /CaH 2 , LiAlH 4 /LiNH 2 , and LiBH 4 /LiNH 2 . [6,7] However, the dehydrogenation of composite materials usually consists of multiple steps associated with relatively poor kinetics, which originate from interfacial reactions, nucleation/nuclei growth, diffusion processes, and so on. [8] Therefore, pursuing appropriate catalysts or additives is crucial to ensure that such materials are viable practically.…”

Section: Introductionmentioning

confidence: 99%

Solid–Solid Heterogeneous Catalysis: The Role of Potassium in Promoting the Dehydrogenation of the Mg(NH₂)₂/2 LiH Composite

et al. 2013

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Considerable efforts have been devoted to the catalytic modification of hydrogen storage materials. The K‐modified Mg(NH2)2/2 LiH composite is a typical model for such studies. In this work, we analyze the origin of the kinetic barrier in the first step of the dehydrogenation and investigate how K catalyzes this heterogeneous solid‐state reaction. Our results indicate that the interface reaction of Mg(NH2)2 and LiH is the main source of the kinetic barrier at the early stage of the dehydrogenation for the intensively ball‐milled Mg(NH2)2/2 LiH sample. K can effectively activate Mg(NH2)2 as well as promote LiH to participate in the dehydrogenation. Three K species of KH, K2Mg(NH2)4, and Li3K(NH2)4 likely transform circularly in the dehydrogenation (KH↔K2Mg(NH2)4↔KLi3(NH2)4), which creates a more energy‐favorable pathway and thus leads to the overall kinetic enhancement. This catalytic role of K in the amide/hydride system is different from the conventional catalysis of transition metals in the alanate system.

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“…In view of their high theoretical hydrogen storage capacities, metal borohydrides have recently been the subject of intensive investigation. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] The dehydrogenation of lithium and Group II borohydrides is plagued by severe kinetic limitations and irreversibility that precludes the utilization of these compounds under practical conditions, [2][3][4][5][6][7][8][9][10] even as components of binary hydride mixtures. [12][13][14][15][16][17][18] Many transition metal borohydride complexes also have suitable gravimetric hydrogen densities.…”

Section: Introductionmentioning

confidence: 99%

LiSc(BH₄)₄: A Novel Salt of Li⁺ and Discrete Sc(BH₄)₄⁻ Complex Anions

et al. 2008

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LiSc(BH 4 ) 4 has been prepared by ball milling of LiBH 4 and ScCl 3 . Vibrational spectroscopy indicates the presence of discrete Sc(BH 4 ) 4 -ions. DFT calculations of this isolated complex ion confirm that it is a stable complex, and the calculated vibrational spectra agree well with the experimental ones. The four BH 4 -groups are oriented with a tilted plane of three hydrogen atoms directed to the central Sc ion, resulting in a global 8 + 4 coordination. The crystal structure obtained by high-resolution synchrotron powder diffraction reveals a tetragonal unit cell with a ) 6.076 Å and c ) 12.034 Å (space group P-42c). The local structure of the Sc(BH 4 ) 4 -complex is refined as a distorted form of the theoretical structure. The Li ions are found to be disordered along the z axis.

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Complex Hydrides for Hydrogen Storage

Cited by 2,049 publications

References 244 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

Solid–Solid Heterogeneous Catalysis: The Role of Potassium in Promoting the Dehydrogenation of the Mg(NH₂)₂/2 LiH Composite

LiSc(BH₄)₄: A Novel Salt of Li⁺ and Discrete Sc(BH₄)₄⁻ Complex Anions

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Complex Hydrides for Hydrogen Storage

Cited by 2,049 publications

References 244 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

Solid–Solid Heterogeneous Catalysis: The Role of Potassium in Promoting the Dehydrogenation of the Mg(NH2)2/2 LiH Composite

LiSc(BH4)4: A Novel Salt of Li+ and Discrete Sc(BH4)4− Complex Anions

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Solid–Solid Heterogeneous Catalysis: The Role of Potassium in Promoting the Dehydrogenation of the Mg(NH₂)₂/2 LiH Composite

LiSc(BH₄)₄: A Novel Salt of Li⁺ and Discrete Sc(BH₄)₄⁻ Complex Anions