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Special Issue "Hydrogen Storage Materials"

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Energy Materials".

Deadline for manuscript submissions: closed (31 March 2015)

Special Issue Editor

Guest Editor
Prof. Dr. Umit B. Demirci

IEM (Institut Europeen des Membranes), UMR 5635 (CNRS-ENSCM-UM2), Universite Montpellier 2, Place E. Bataillon, F-34095, Montpellier, France
Website | E-Mail
Fax: +33(0)4.67.14.91.19
Interests: Boranes; Boron- and nitrogen-based materials; Chemical hydrogen storage; Hydrolytic and thermolytic dehydrogenation; Heterogeneous (metal) catalysis

Special Issue Information

Dear Colleagues,

Over the past decade, the field of hydrogen storage has been significantly “energized” through the emergence of hydrogen storage materials. Under societal, economic and environmental pressure, scientists all over the world have shown dynamism, creativity and innovation and have “discovered” a large number of storage solutions, namely of hydrogen storage materials.

We all agree that one of the key issues hindering the development of a near-future hydrogen economy is hydrogen storage... We all agree that the efforts dedicated to address this issue are commensurate with its importance... Actually, we all agree on these because our common ultimate objective is to propose and develop viable solutions for many technological applications, from stationary to niche ones, via vehicular, mobile and portable.

In this context, the main focus of the forthcoming “hydrogen storage materials” special issue is to present a comprehensive overview of the new developments in the field. Recent advances in the science and technology of (i) the materials enabling physical adsorption of molecular hydrogen (i.e. sorbents for [cryo-]adsorption) and (ii) the materials for liquid-/solid-state chemical hydrogen storage (i.e. hydrides, amine-boranes, amides/imides, hydrocarbons/organic heterocycles, hydrous hydrazine, etc.) will be addressed.

It is my pleasure to invite you to submit a manuscript for this special issue. Full papers, communications, and reviews are all welcome.

Umit B. DEMIRCI
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1500 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.


Keywords

  • hydrogen storage material
  • physical storage
  • sorbent for cryo-adsorption
  • chemical storage
  • amide/imide
  • borane
  • hydrous hydrazine
  • hydride
  • hydrogen carrier
  • organic heterocycles

Published Papers (11 papers)

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Research

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Open AccessArticle Hydrogenation Properties of TiFe Doped with Zirconium
Materials 2015, 8(11), 7864-7872; doi:10.3390/ma8115423
Received: 26 August 2015 / Revised: 11 November 2015 / Accepted: 12 November 2015 / Published: 20 November 2015
Cited by 4 | PDF Full-text (6795 KB) | HTML Full-text | XML Full-text
Abstract
The goal of this study was to optimize the activation behaviour of hydrogen storage alloy TiFe. We found that the addition of a small amount of Zr in TiFe alloy greatly reduces the hydrogenation activation time. Two different procedural synthesis methods were applied:
[...] Read more.
The goal of this study was to optimize the activation behaviour of hydrogen storage alloy TiFe. We found that the addition of a small amount of Zr in TiFe alloy greatly reduces the hydrogenation activation time. Two different procedural synthesis methods were applied: co-melt, where the TiFe was melted and afterward re-melted with the addition of Zr, and single-melt, where Ti, Fe and Zr were melted together in one single operation. The co-melted sample absorbed hydrogen at its maximum capacity in less than three hours without any pre-treatment. The single-melted alloy absorbed its maximum capacity in less than seven hours, also without pre-treatment. The reason for discrepancies between co-melt and single-melt alloys was found to be the different microstructure. The effect of air exposure was also investigated. We found that the air-exposed samples had the same maximum capacity as the argon protected samples but with a slightly longer incubation time, which is probably due to the presence of a dense surface oxide layer. Scanning electron microscopy revealed the presence of a rich Zr intergranular phase in the TiFe matrix, which is responsible for the enhanced hydrogenation properties of these Zr-doped TiFe alloys. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
Open AccessArticle Synthesis of Ternary Borocarbonitrides by High Temperature Pyrolysis of Ethane 1,2-Diamineborane
Materials 2015, 8(9), 5974-5985; doi:10.3390/ma8095285
Received: 26 May 2015 / Revised: 14 August 2015 / Accepted: 24 August 2015 / Published: 9 September 2015
Cited by 3 | PDF Full-text (1546 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Ethane 1,2-diamineborane (EDAB) is an alkyl-containing amine-borane adduct with improved hydrogen desorption properties as compared to ammonia borane. In this work, it is reported the high temperature thermolytic decomposition of EDAB. Thermolysis of EDAB has been investigated by concomitant thermogravimetry-differential thermal analysis-mass spectrometry
[...] Read more.
Ethane 1,2-diamineborane (EDAB) is an alkyl-containing amine-borane adduct with improved hydrogen desorption properties as compared to ammonia borane. In this work, it is reported the high temperature thermolytic decomposition of EDAB. Thermolysis of EDAB has been investigated by concomitant thermogravimetry-differential thermal analysis-mass spectrometry experiments. EDAB shows up to four H2 desorption events below 1000 °C. Small fractions of CH4, C2H4 and CO/CO2 are also observed at moderate-high temperatures. The solid-state thermolysis product has been characterized by means of different structural and chemical methods, such as X-ray diffraction, Raman spectroscopy, Scanning electron microscopy, Elemental analysis, and X-ray photoelectron spectroscopy (XPS). The obtained results indicate the formation of a ternary borocarbonitride compound with a poorly-crystalline graphitic-like structure. By contrast, XPS measurements show that the surface is rich in carbon and nitrogen oxides, which is quite different to the bulk of the material. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
Open AccessArticle Dihydrogen Phosphate Stabilized Ruthenium(0) Nanoparticles: Efficient Nanocatalyst for The Hydrolysis of Ammonia-Borane at Room Temperature
Materials 2015, 8(7), 4226-4238; doi:10.3390/ma8074226
Received: 29 May 2015 / Revised: 1 July 2015 / Accepted: 7 July 2015 / Published: 10 July 2015
Cited by 4 | PDF Full-text (513 KB) | HTML Full-text | XML Full-text
Abstract
Intensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution
[...] Read more.
Intensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution under mild conditions in the presence of a suitable catalyst. Herein, we report the synthesis of ruthenium(0) nanoparticles stabilized by dihydrogenphosphate anions with an average particle size of 2.9 ± 0.9 nm acting as a water-dispersible nanocatalyst in the hydrolysis of ammonia-borane. They provide an initial turnover frequency (TOF) value of 80 min−1 in hydrogen generation from the hydrolysis of ammonia-borane at room temperature. Moreover, the high stability of these ruthenium(0) nanoparticles makes them long-lived and reusable nanocatalysts for the hydrolysis of ammonia-borane. They provide 56,800 total turnovers and retain ~80% of their initial activity even at the fifth catalytic run in the hydrolysis of ammonia-borane at room temperature. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
Open AccessArticle Kinetic Modification on Hydrogen Desorption of Lithium Hydride and Magnesium Amide System
Materials 2015, 8(7), 3896-3909; doi:10.3390/ma8073896
Received: 25 April 2015 / Revised: 3 June 2015 / Accepted: 9 June 2015 / Published: 29 June 2015
Cited by 3 | PDF Full-text (579 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Various synthesis and rehydrogenation processes of lithium hydride (LiH) and magnesium amide (Mg(NH2)2) system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a
[...] Read more.
Various synthesis and rehydrogenation processes of lithium hydride (LiH) and magnesium amide (Mg(NH2)2) system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a solid-solid reaction, it is expected that the kinetic properties become worse by the sintering and phase separation. In fact, it is experimentally found that the low crystalline size and the close contact of LiH and Mg(NH2)2 lead to the fast hydrogen desorption. To preserve the potential hydrogen desorption properties, thermochemical and mechanochemical rehydrogenation processes are investigated. Although the only thermochemical process results in slowing the reaction rate due to the crystallization, the ball-milling can recover the original hydrogen desorption properties. Furthermore, the mechanochemical process at 150 °C is useful as the rehydrogenation technique to preserve the suitable crystalline size and mixing state of the reactants. As a result, it is demonstrated that the 8LiH and 3Mg(NH2)2 system is recognized as the potential hydrogen storage material to desorb more than 5.5 mass% of H2 at 150 °C. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
Open AccessArticle Catalytically Enhanced Hydrogen Sorption in Mg-MgH2 by Coupling Vanadium-Based Catalyst and Carbon Nanotubes
Materials 2015, 8(6), 3491-3507; doi:10.3390/ma8063491
Received: 31 March 2015 / Revised: 2 June 2015 / Accepted: 4 June 2015 / Published: 12 June 2015
Cited by 7 | PDF Full-text (2347 KB) | HTML Full-text | XML Full-text
Abstract
Mg (MgH2)-based composites, using carbon nanotubes (CNTs) and pre-synthesized vanadium-based complex (VCat) as the catalysts, were prepared by high-energy ball milling technique. The synergistic effect of coupling CNTs and VCat in MgH2 was observed for an ultra-fast absorption rate of
[...] Read more.
Mg (MgH2)-based composites, using carbon nanotubes (CNTs) and pre-synthesized vanadium-based complex (VCat) as the catalysts, were prepared by high-energy ball milling technique. The synergistic effect of coupling CNTs and VCat in MgH2 was observed for an ultra-fast absorption rate of 6.50 wt. % of hydrogen per minute and 6.50 wt. % of hydrogen release in 10 min at 200 °C and 300 °C, respectively. The temperature programmed desorption (TPD) results reveal that coupling VCat and CNTs reduces both peak and onset temperatures by more than 60 °C and 114 °C, respectively. In addition, the presence of both VCat and CNTs reduces the enthalpy and entropy of desorption of about 7 kJ/mol H2 and 11 J/mol H2·K, respectively, as compared to those of the commercial MgH2, which ascribe to the decrease of desorption temperature. From the study of the effect of CNTs milling time, it is shown that partially destroyed CNTs (shorter milling time) are better to enhance the hydrogen sorption performance. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
Open AccessArticle Mechanical and Thermal Dehydrogenation of the Mechano-Chemically Synthesized Calcium Alanate (Ca(AlH4)2) and Lithium Chloride (LiCl) Composite
Materials 2015, 8(6), 3479-3490; doi:10.3390/ma8063479
Received: 24 March 2015 / Revised: 4 June 2015 / Accepted: 5 June 2015 / Published: 12 June 2015
Cited by 1 | PDF Full-text (1973 KB) | HTML Full-text | XML Full-text
Abstract
LiAlH4 and CaCl2 were employed for mechano-chemical activation synthesis (MCAS) of Ca(AlH4)2 and LiCl hydride composite. After short ball milling time, their X-ray diffraction (XRD) peaks are clearly observed. After ball milling for a longer duration than 0.5
[...] Read more.
LiAlH4 and CaCl2 were employed for mechano-chemical activation synthesis (MCAS) of Ca(AlH4)2 and LiCl hydride composite. After short ball milling time, their X-ray diffraction (XRD) peaks are clearly observed. After ball milling for a longer duration than 0.5 h, the CaAlH5 diffraction peaks are observed which indicates that Ca(AlH4)2 starts decomposing during ball milling into CaAlH5+Al+1.5H2. It is estimated that less than 1 wt % H2 was mechanically dehydrogenated in association with decomposition reaction. After 2.5 h of ball milling, no Ca(AlH4)2 diffraction peaks were observed on XRD patterns which suggests that Ca(AlH4)2 was decomposed. Thermal behavior of ball milled powders, which was investigated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), indicates that a certain fraction of Ca(AlH4)2 could have been disordered/amorphized during ball milling being undetectable by XRD. The apparent activation energy for the decomposition of Ca(AlH4)2 and CaAlH5 equals 135 kJ/mol and 183 kJ/mol, respectively. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
Open AccessArticle The Concept about the Regeneration of Spent Borohydrides and Used Catalysts from Green Electricity
Materials 2015, 8(6), 3456-3466; doi:10.3390/ma8063456
Received: 15 March 2015 / Revised: 31 May 2015 / Accepted: 3 June 2015 / Published: 10 June 2015
Cited by 1 | PDF Full-text (1560 KB) | HTML Full-text | XML Full-text
Abstract
Currently, the Brown-Schlesinger process is still regarded as the most common and mature method for the commercial production of sodium borohydride (NaBH4). However, the metallic sodium, currently produced from the electrolysis of molten NaCl that is mass-produced by evaporation of seawater
[...] Read more.
Currently, the Brown-Schlesinger process is still regarded as the most common and mature method for the commercial production of sodium borohydride (NaBH4). However, the metallic sodium, currently produced from the electrolysis of molten NaCl that is mass-produced by evaporation of seawater or brine, is probably the most costly raw material. Recently, several reports have demonstrated the feasibility of utilizing green electricity such as offshore wind power to produce metallic sodium through electrolysis of seawater. Based on this concept, we have made improvements and modified our previously proposed life cycle of sodium borohydride (NaBH4) and ammonia borane (NH3BH3), in order to further reduce costs in the conventional Brown-Schlesinger process. In summary, the revision in the concept combining the regeneration of the spent borohydrides and the used catalysts with the green electricity is reflected in (1) that metallic sodium could be produced from NaCl of high purity obtained from the conversion of the byproduct in the synthesis of NH3BH3 to devoid the complicated purification procedures if produced from seawater; and (2) that the recycling and the regeneration processes of the spent NaBH4 and NH3BH3 as well as the used catalysts could be simultaneously carried out and combined with the proposed life cycle of borohydrides. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
Open AccessArticle Ru-N-C Hybrid Nanocomposite for Ammonia Dehydrogenation: Influence of N-doping on Catalytic Activity
Materials 2015, 8(6), 3442-3455; doi:10.3390/ma8063442
Received: 19 April 2015 / Revised: 29 May 2015 / Accepted: 3 June 2015 / Published: 10 June 2015
Cited by 7 | PDF Full-text (2014 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
For application to ammonia dehydrogenation, novel Ru-based heterogeneous catalysts, Ru-N-C and Ru-C, were synthesized via simple pyrolysis of a mixture of RuCl3·6H2O and carbon black with or without dicyandiamide as a nitrogen-containing precursor at 550 °C. Characterization of the
[...] Read more.
For application to ammonia dehydrogenation, novel Ru-based heterogeneous catalysts, Ru-N-C and Ru-C, were synthesized via simple pyrolysis of a mixture of RuCl3·6H2O and carbon black with or without dicyandiamide as a nitrogen-containing precursor at 550 °C. Characterization of the prepared Ru-N-C and Ru-C catalysts via scanning transmission electron microscopy, in conjunction with energy dispersive X-ray spectroscopy, indicated the formation of hollow nanocomposites in which the average sizes of the Ru nanoparticles were 1.3 nm and 5.1 nm, respectively. Compared to Ru-C, the Ru-N-C nanocomposites not only proved to be highly active for ammonia dehydrogenation, giving rise to a NH3 conversion of >99% at 550 °C, but also exhibited high durability. X-ray photoelectron spectroscopy revealed that the Ru active sites in Ru-N-C were electronically perturbed by the incorporated nitrogen atoms, which increased the Ru electron density and ultimately enhanced the catalyst activity. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
Open AccessArticle Revisiting the Hydrogen Storage Behavior of the Na-O-H System
Materials 2015, 8(5), 2191-2203; doi:10.3390/ma8052191
Received: 19 February 2015 / Revised: 20 April 2015 / Accepted: 22 April 2015 / Published: 28 April 2015
Cited by 2 | PDF Full-text (977 KB) | HTML Full-text | XML Full-text
Abstract
Solid-state reactions between sodium hydride and sodium hydroxide are unusual among hydride-hydroxide systems since hydrogen can be stored reversibly. In order to understand the relationship between hydrogen uptake/release properties and phase/structure evolution, the dehydrogenation and hydrogenation behavior of the Na-O-H system has been
[...] Read more.
Solid-state reactions between sodium hydride and sodium hydroxide are unusual among hydride-hydroxide systems since hydrogen can be stored reversibly. In order to understand the relationship between hydrogen uptake/release properties and phase/structure evolution, the dehydrogenation and hydrogenation behavior of the Na-O-H system has been investigated in detail both ex- and in-situ. Simultaneous thermogravimetric-differential thermal analysis coupled to mass spectrometry (TG-DTA-MS) experiments of NaH-NaOH composites reveal two principal features: Firstly, an H2 desorption event occurring between 240 and 380 °C and secondly an additional endothermic process at around 170 °C with no associated weight change. In-situ high-resolution synchrotron powder X-ray diffraction showed that NaOH appears to form a solid solution with NaH yielding a new cubic complex hydride phase below 200 °C. The Na-H-OH phase persists up to the maximum temperature of the in-situ diffraction experiment shortly before dehydrogenation occurs. The present work suggests that not only is the inter-phase synergic interaction of protic hydrogen (in NaOH) and hydridic hydrogen (in NaH) important in the dehydrogenation mechanism, but that also an intra-phase Hδ+… Hδ– interaction may be a crucial step in the desorption process. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
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Review

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Open AccessReview Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides
Materials 2015, 8(9), 5891-5921; doi:10.3390/ma8095280
Received: 29 July 2015 / Revised: 18 August 2015 / Accepted: 19 August 2015 / Published: 4 September 2015
Cited by 13 | PDF Full-text (2721 KB) | HTML Full-text | XML Full-text
Abstract
This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems
[...] Read more.
This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM) fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
Open AccessReview Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane
Materials 2015, 8(7), 4512-4534; doi:10.3390/ma8074512
Received: 6 May 2015 / Revised: 6 May 2015 / Accepted: 15 July 2015 / Published: 21 July 2015
Cited by 6 | PDF Full-text (1668 KB) | HTML Full-text | XML Full-text
Abstract
Hydrogen storage is still one of the most significant issues hindering the development of a “hydrogen energy economy”. Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of
[...] Read more.
Hydrogen storage is still one of the most significant issues hindering the development of a “hydrogen energy economy”. Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based catalyst. The reaction performance depends on the morphology and/or structure of these materials. In this review, we survey the research on nanostructured materials, especially porous materials for hydrogen generation from hydrolysis of ammonia borane. Full article
(This article belongs to the Special Issue Hydrogen Storage Materials)
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