Reversibility of the hydrogen desorption from LiBH4: a synergetic effect of nanoconfinement and Ni addition

Ngene, Peter; Zwienen, Mart van; Jongh, Petra E. de

doi:10.1039/c0cc03218b

Cited by 132 publications

(129 citation statements)

References 19 publications

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“…Furthermore, using XRD, reversible Li intercalation has been demonstrated earlier in these samples. 11,30 Therefore if reaction (3a) or (3b) did occur to some extent, the lithium is likely intercalated in the carbon. Unfortunately, we do not know how the Li K-edge XRS features of intercalated lithium will look like in the present carbon nanoframework and therefore we do not know its features in Li XRS, but we expect that this is also present in Li XRS spectrum of the LiBH 4 -C deh due to the broader band area between 60 and 62 eV.…”

Section: Resultsmentioning

confidence: 99%

“…11,12 During and after de-hydrogenation, the LiBH 4 -C decomposes mainly in LiH and boron and there is also a substantial amount of Li 2 B 12 H 12 .…”

Section: Discussionmentioning

confidence: 99%

“…[5][6][7][8][9][10][11][12][13][14][15] These strategies generally led to an improvement in their hydrogen sorption properties. However, for practical application further improvement of these materials is required.…”

Section: Introductionmentioning

confidence: 99%

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In situ X-ray Raman spectroscopy study of the hydrogen sorption properties of lithium borohydride nanocomposites

Miedema

Ngene

Eerden

et al. 2014

Phys. Chem. Chem. Phys.

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Nanoconfined alkali metal borohydrides are promising materials for reversible hydrogen storage applications, but the characterization of hydrogen sorption in these materials is difficult. Here we show that with in situ X-ray Raman spectroscopy (XRS) we can track the relative amounts of intermediates and final products formed during de-and re-hydrogenation of nanoconfined lithium borohydride (LiBH 4 ) and therefore we can possibly identify the de-and re-hydrogenation pathways. In the XRS of nanoconfined LiBH 4 at different points in the de-and re-hydrogenation, we identified phases that lead to the conclusion that de-and re-hydrogenation pathways in nanoconfined LiBH 4 are different from bulk LiBH 4 : intercalated lithium (LiC x ), boron and lithium hydride were formed during de-hydrogenation, but as well Li 2 B 12 H 12 was observed indicating that there is possibly some bulk LiBH 4 present in the nanoconfined sample LiBH 4 -C as prepared.Surprisingly, XRS revealed that the de-hydrogenated products of the LiBH 4 -C nanocomposites can be partially rehydrogenated to about 90% of Li 2 B 12 H 12 and 2-5% of LiBH 4 at a mild condition of 1 bar H 2 and 350 1C. This suggests that re-hydrogenation occurs via the formation of Li 2 B 12 H 12 . Our results show that XRS is an elegant technique that can be used for in and ex situ study of the hydrogen sorption properties of nanoconfined and bulk light-weight metal hydrides in energy storage applications.

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Section: Resultsmentioning

confidence: 99%

“…11,12 During and after de-hydrogenation, the LiBH 4 -C decomposes mainly in LiH and boron and there is also a substantial amount of Li 2 B 12 H 12 .…”

Section: Discussionmentioning

confidence: 99%

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In situ X-ray Raman spectroscopy study of the hydrogen sorption properties of lithium borohydride nanocomposites

Miedema

Ngene

Eerden

et al. 2014

Phys. Chem. Chem. Phys.

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“…However an investigation of the hydrogen uptake behaviour in the nanocomposites show that the nickel boride does not only enhance the overall uptake rates but its presence also seems to increase the fraction of the material that can be rehydrogenated under mild conditions. 29 Other possible roles of nickel boride in the nanocomposite could be to act as a nucleation site for the reversible formation of LiBH 4 from the dehydrogenated products, and/or that its presence influences the microstructure of the nanocomposites during desorption and rehydrogenation.…”

Section: Characterization Of the Ni Chemical Environmentmentioning

confidence: 99%

“…29 In this paper we discuss how Ni nanoparticles increase the reversibility of the hydrogen desorption. Although Ni is a classical hydrogenation catalyst, for complex metal hydrides usually the dissociation of hydrogen molecules at the surface is not the rate limiting factor.…”

Section: Introductionmentioning

confidence: 99%

The role of Ni in increasing the reversibility of the hydrogen release from nanoconfined LiBH4

Ngene

Verkuijlen²,

Zheng

et al. 2011

Faraday Discuss.

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Nanoconfinement and the use of catalysts are promising strategies to enhance the reversibility of hydrogen storage in light metal hydrides. We combined nanoconfinement of LiBH 4 in nanoporous carbon with the addition of Ni. Samples were prepared by deposition of 5-6 nm Ni nanoparticles inside the porous carbon, followed by melt infiltration with LiBH 4 . The Ni addition has only a slight influence on the LiBH 4 hydrogen desorption, but significantly enhances the subsequent uptake of hydrogen under mild conditions. Reversible, but limited, intercalation of Li is observed during hydrogen cycling. X-ray diffraction shows that the initial crystalline 5-6 nm Ni nanoparticles are not present anymore after melt infiltration with LiBH 4 . However, transmission electron microscopy showed Ni-containing nanoparticles in the samples. Extended X-ray absorption fine structure spectroscopy proved the presence of Ni x B phases with the Ni-B coordination numbers changing reversibly with dehydrogenation and rehydrogenation of the sample. Ni x B can act as a hydrogenation catalyst, but solid-state 11 B NMR proved that the addition of Ni also enhanced the reversibility of the system by influencing the microstructure of the nanoconfined LiBH 4 upon cycling.

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The Size Dependence of Hydrogen Mobility and Sorption Kinetics for Carbon‐Supported MgH₂ Particles

Obbink

Srinivasan

et al. 2014

Adv Funct Materials

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112

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MgH 2 is a promising material for reversible solid-state hydrogen storage. It is known that particle size can have a strong impact on hydrogen dynamics and sorption characteristics, but more detailed insight has been hampered by the great challenge to prepare small and well-defi ned particles and study their hydrogen storage properties upon cycling. The preparation of MgH 2 nanoparticles supported on high surface area carbon aerogels with pore sizes varying from 6-20 nm is reported. Two distinctly different MgH 2 particle populations are observed: X-ray diffraction invisible nanoparticles with sizes below 20 nm, and larger, crystalline, MgH 2 particles. They release hydrogen at temperatures 140 °C lower than bulk MgH 2 . The size-dependent hydrogen kinetics is for the fi rst time corroborated by intrinsic hydrogen dynamics data obtained by solid state 1 H NMR. Fast cycling is possible (80% of the capacity absorbed within 15 min at 18 bar and 300 °C), without a change in the hydrogen sorption properties, showing that the growth of the nanoparticles is effectively prevented by the carbon support. A clear correlation is found between the hydrogen desorption temperature and the size of the MgH 2 nanoparticles. This illustrates the potential of the use of supported nanoparticles for fast, reversible, and stable hydrogen cycling.

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Reversibility of the hydrogen desorption from LiBH4: a synergetic effect of nanoconfinement and Ni addition

Abstract: The reversible hydrogen capacity of LiBH 4 was improved by a combination of Ni addition, nanosizing and confinement of the active phase in a nanoporous carbon scaffold.

Cited by 132 publications

References 19 publications

In situ X-ray Raman spectroscopy study of the hydrogen sorption properties of lithium borohydride nanocomposites

In situ X-ray Raman spectroscopy study of the hydrogen sorption properties of lithium borohydride nanocomposites

The role of Ni in increasing the reversibility of the hydrogen release from nanoconfined LiBH4

The Size Dependence of Hydrogen Mobility and Sorption Kinetics for Carbon‐Supported MgH₂ Particles

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Reversibility of the hydrogen desorption from LiBH4: a synergetic effect of nanoconfinement and Ni addition

Abstract: The reversible hydrogen capacity of LiBH 4 was improved by a combination of Ni addition, nanosizing and confinement of the active phase in a nanoporous carbon scaffold.

Cited by 132 publications

References 19 publications

In situ X-ray Raman spectroscopy study of the hydrogen sorption properties of lithium borohydride nanocomposites

In situ X-ray Raman spectroscopy study of the hydrogen sorption properties of lithium borohydride nanocomposites

The role of Ni in increasing the reversibility of the hydrogen release from nanoconfined LiBH4

The Size Dependence of Hydrogen Mobility and Sorption Kinetics for Carbon‐Supported MgH2 Particles

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The Size Dependence of Hydrogen Mobility and Sorption Kinetics for Carbon‐Supported MgH₂ Particles