Hydrogen Storage Alloys

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Inorganic Crystalline Materials".

Deadline for manuscript submissions: closed (31 January 2012) | Viewed by 86317

Special Issue Editor

Department of Physical Chemistry, University of Geneva - Sciences II, 30 quai Ernest-Ansermet, 1211 Geneva 4, Switzerland
Interests: crystal chemistry and optical and vibrational spectroscopy in rare-earth doped insulators (halides, oxides) as well as on compounds with borohydrides as potential hydrogen storage materials
Special Issues, Collections and Topics in MDPI journals

Keywords

  • complex and metallic hydrides
  • borohydrides
  • alanates and aluminum hydride
  • aminoboranes
  • amides
  • amines
  • reactive composites
  • MOF
  • hydrogen storage alloy
  • Mg-based alloy
  • rare-earth element based alloy
  • crystal structure
  • hydrogen storage material
  • anode
  • hydrogen diffusion
  • hydrogen storage properties

Published Papers (11 papers)

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Research

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2262 KiB  
Article
Hydrogen Desorption from Mg Hydride: An Ab Initio Study
by Simone Giusepponi and Massimo Celino
Crystals 2012, 2(3), 845-860; https://doi.org/10.3390/cryst2030845 - 04 Jul 2012
Cited by 11 | Viewed by 6461
Abstract
Hydrogen desorption from hydride matrix is still an open field of research. By means of accurate first-principle molecular dynamics (MD) simulations an Mg–MgH2 interface is selected, studied and characterized. Electronic structure calculations are used to determine the equilibrium properties and the behavior of [...] Read more.
Hydrogen desorption from hydride matrix is still an open field of research. By means of accurate first-principle molecular dynamics (MD) simulations an Mg–MgH2 interface is selected, studied and characterized. Electronic structure calculations are used to determine the equilibrium properties and the behavior of the surfaces in terms of structural deformations and total energy considerations. Furthermore, extensive ab-initio molecular dynamics simulations are performed at several temperatures to characterize the desorption process at the interface. The numerical model successfully reproduces the experimental desorption temperature for the hydride. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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1170 KiB  
Article
Thermodynamic Properties, Hysteresis Behavior and Stress-Strain Analysis of MgH2 Thin Films, Studied over a Wide Temperature Range
by Yevheniy Pivak, Herman Schreuders and Bernard Dam
Crystals 2012, 2(2), 710-729; https://doi.org/10.3390/cryst2020710 - 20 Jun 2012
Cited by 21 | Viewed by 7419
Abstract
Using hydrogenography, we investigate the thermodynamic parameters and hysteresis behavior in Mg thin films capped by Ta/Pd, in a temperature range from 333 K to 545 K. The enthalpy and entropy of hydride decomposition, ∆Hdes = −78.3 kJ/molH2, [...] Read more.
Using hydrogenography, we investigate the thermodynamic parameters and hysteresis behavior in Mg thin films capped by Ta/Pd, in a temperature range from 333 K to 545 K. The enthalpy and entropy of hydride decomposition, ∆Hdes = −78.3 kJ/molH2, Sdes = −136.1 J/K molH2, estimated from the Van't Hoff analysis, are in good agreement with bulk results, while the absorption thermodynamics, ∆Habs = −61.6 kJ/molH2, ∆Sabs = −110.9 J/K molH2, appear to be substantially affected by the clamping of the film to the substrate. The clamping is negligible at high temperatures, T > 523 K, while at lower temperatures, T < 393 K, it is considerable. The hysteresis at room temperature in Mg/Ta/Pd films increases by a factor of 16 as compared to MgH2 bulk. The hysteresis increases even further in Mg/Pd films, most likely due to the formation of a Mg-Pd alloy at the Mg/Pd interface. The stress–strain analysis of the Mg/Ta/Pd films at 300–333 K proves that the increase of the hysteresis occurs due to additional mechanical work during the (de-)hydrogenation cycle. With a proper temperature correction, our stress–strain analysis quantitatively and qualitatively explains the hysteresis behavior in thin films, as compared to bulk, over the whole temperature range. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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1679 KiB  
Article
Silica-Metal Composite for Hydrogen Storage Applications
by Marzia Pentimalli, Enrico Imperi, Mariangela Bellusci, Carlo Alvani, Andrea Santini and Franco Padella
Crystals 2012, 2(2), 690-703; https://doi.org/10.3390/cryst2020690 - 18 Jun 2012
Cited by 7 | Viewed by 6374
Abstract
In spite of their favourable chemical characteristics, using AB5 alloys as fixed bed for hydrogen storage devices requires proper management of a number of technological aspects. Among these, the mechanical stability of metal particle grains under hydrogen cycling and the overall thermal conductivity [...] Read more.
In spite of their favourable chemical characteristics, using AB5 alloys as fixed bed for hydrogen storage devices requires proper management of a number of technological aspects. Among these, the mechanical stability of metal particle grains under hydrogen cycling and the overall thermal conductivity of the material bed constitute crucial features. We developed by High Energy Ball Milling HEBM a mechanically stable silica-based AB5 composite with enhanced thermal conductivity. Here, focusing on the material’s physical-chemical properties, we report on the silica-AB5 composite development and characterization. Particularly, we studied the material consolidation process, the resulting composite morphology and the system behaviour under hydrogen loading/unloading cycling. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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556 KiB  
Article
Ammonia Uptake and Release in the MnX2–NH3 (X = Cl, Br) Systems and Structure of the Mn(NH3)nX2 (n = 6, 2) Ammines
by Hazel Reardon, James M. Hanlon, Michael Grant, Imogen Fullbrook and Duncan H. Gregory
Crystals 2012, 2(2), 193-212; https://doi.org/10.3390/cryst2020193 - 10 Apr 2012
Cited by 24 | Viewed by 9017
Abstract
Hexa-ammine complexes, Mn(NH3)6X2 (X = Cl, Br), have been synthesized by ammoniation of the corresponding transition metal halide and characterized by Powder X-ray diffraction (PXRD) and Raman spectroscopy. The hexa-ammine complexes are isostructural (Cubic, Fm-3m [...] Read more.
Hexa-ammine complexes, Mn(NH3)6X2 (X = Cl, Br), have been synthesized by ammoniation of the corresponding transition metal halide and characterized by Powder X-ray diffraction (PXRD) and Raman spectroscopy. The hexa-ammine complexes are isostructural (Cubic, Fm-3m, Z = 4; a = 10.2742(6) Å and 10.527(1) Å for X = Cl, Br respectively). Temperature programmed desorption (TPD) demonstrated that ammonia release from Mn(NH3)6X2 complexes occurred in three stages corresponding to the release of 4, 1 and 1 NH3 equivalents respectively. The chloride and bromide both exhibit a deammoniation onset temperature below 323 K. The di-ammoniates from the first desorption step were isolated during TPD measurements and their crystal structures determined by Rietveld refinement against PXRD data (X = Cl: orthorhombic Cmmm, a = 8.1991(9) Å, b = 8.2498(7) Å, c = 3.8212(4) Å, Z = 2; X = Br: orthorhombic Pbam, a = 6.0109(5) Å, b = 12.022(1) Å, c = 4.0230(2) Å, Z = 2). Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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532 KiB  
Article
Mechanical and Thermal Dehydrogenation of Lithium Alanate (LiAlH4) and Lithium Amide (LiNH2) Hydride Composites
by Robert A. Varin and Leszek Zbroniec
Crystals 2012, 2(2), 159-175; https://doi.org/10.3390/cryst2020159 - 02 Apr 2012
Cited by 11 | Viewed by 5788
Abstract
Hydrogen storage properties of the (nLiAlH4 + LiNH2) hydride composite where n = 1, 3, 11.5 and 30, synthesized by high energy ball milling have been investigated. The composite with the molar ratio n = 1 releases large quantities of [...] Read more.
Hydrogen storage properties of the (nLiAlH4 + LiNH2) hydride composite where n = 1, 3, 11.5 and 30, synthesized by high energy ball milling have been investigated. The composite with the molar ratio n = 1 releases large quantities of H2 (up to ~5 wt.%) during ball milling up to 100–150 min. The quantity of released H2 rapidly decreases for the molar ratio n = 3 and is not observed for n = 11.5 and 30. The XRD studies indicate that the H2 release is a result of a solid state decomposition of LiAlH4 into (1/3)Li3AlH6 + (2/3)Al + H2 and subsequently decomposition of (1/3)Li3AlH6 into LiH + (1/3)Al + 0.5H2. Apparently, LiAlH4 is profoundly destabilized during ball milling by the presence of a large quantity of LiNH2 (37.7 wt.%) in the n = 1 composite. The rate of dehydrogenation at 100–170 °C (at 1 bar H2) is adversely affected by insufficient microstructural refinement, as observed for the n = 1 composite, which was milled for only 2 min to avoid H2 discharge during milling. XRD studies show that isothermal dehydrogenation of (nLiAlH4 + LiNH2) occurs by the same LiAlH4 decomposition reactions as those found during ball milling. The ball milled n = 1 composite stored under Ar at 80 °C slowly discharges large quantities of H2 approaching 3.5 wt.% after 8 days of storage. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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747 KiB  
Article
Theoretical and Experimental Study of LiBH4-LiCl Solid Solution
by Olena Zavorotynska, Marta Corno, Eugenio Pinatel, Line H. Rude, Piero Ugliengo, Torben R. Jensen and Marcello Baricco
Crystals 2012, 2(1), 144-158; https://doi.org/10.3390/cryst2010144 - 21 Mar 2012
Cited by 30 | Viewed by 6988
Abstract
Anion substitution is at present one of the pathways to destabilize metal borohydrides for solid state hydrogen storage. In this work, a solid solution of LiBH4 and LiCl is studied by density functional theory (DFT) calculations, thermodynamic modeling, X-ray diffraction, and infrared [...] Read more.
Anion substitution is at present one of the pathways to destabilize metal borohydrides for solid state hydrogen storage. In this work, a solid solution of LiBH4 and LiCl is studied by density functional theory (DFT) calculations, thermodynamic modeling, X-ray diffraction, and infrared spectroscopy. It is shown that Cl substitution has minor effects on thermodynamic stability of either the orthorhombic or the hexagonal phase of LiBH4. The transformation into the orthorhombic phase in LiBH4 shortly after annealing with LiCl is for the first time followed by infrared measurements. Our findings are in a good agreement with an experimental study of the LiBH4-LiCl solid solution structure and dynamics. This demonstrates the validity of the adopted combined theoretical (DFT calculations) and experimental (vibrational spectroscopy) approach, to investigate the solid solution formation of complex hydrides. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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446 KiB  
Article
Studies of Modified Hydrogen Storage Intermetallic Compounds Used as Fuel Cell Anodes
by Yun Chen, Diogo M. F. Santos, César A. C. Sequeira and Rui F. M. Lobo
Crystals 2012, 2(1), 22-33; https://doi.org/10.3390/cryst2010022 - 28 Dec 2011
Cited by 5 | Viewed by 6597
Abstract
The possibility of substituting Pt/C with the hydrogen storage alloy MlNi3.6Co0.85Al0.3Mn0.3 as the anode active material of a proton exchange membrane fuel cell system has been analyzed. The electrochemical properties indicate that a much more electrochemically [...] Read more.
The possibility of substituting Pt/C with the hydrogen storage alloy MlNi3.6Co0.85Al0.3Mn0.3 as the anode active material of a proton exchange membrane fuel cell system has been analyzed. The electrochemical properties indicate that a much more electrochemically active anode is obtained by impregnating the active material loaded anode in a Nafion proton conducting polymer. Such performance improvement might result from the increase of three-phase boundary sites or length in the gas diffusion electrode where the electrochemical reaction occurs. The experimental data revealed that the membrane electrode assembly (MEA) shows better results when the anode active material, MlNi3.6Co0.85Al0.3Mn0.3, is treated with a hot alkaline KBH4 solution, and then chemically coated with 3 wt.% Pd. The MEA with the aforesaid modification presents an enhanced surface capability for hydrogen adsorption, and has been studied by molecular beam-thermal desorption spectrometry. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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717 KiB  
Article
Differential Scanning Calorimetry (DSC) and Synchrotron X-ray Diffraction Study of Unmilled and Milled LiBH4: A Partial Release of Hydrogen at Moderate Temperatures
by J. Lang, A. Gerhauser, Y. Filinchuk, T. Klassen and J. Huot
Crystals 2012, 2(1), 1-21; https://doi.org/10.3390/cryst2010001 - 27 Dec 2011
Cited by 11 | Viewed by 6565
Abstract
A systematic investigation of phase transitions in unmilled and milled LiBH4 has been performed by Pressurized Differential Scanning Calorimetry (PDSC). It was found that a large exotherm is present below the low temperature (LT) → high temperature (HT) phase transition. This exotherm [...] Read more.
A systematic investigation of phase transitions in unmilled and milled LiBH4 has been performed by Pressurized Differential Scanning Calorimetry (PDSC). It was found that a large exotherm is present below the low temperature (LT) → high temperature (HT) phase transition. This exotherm is not caused by air contamination but seems to originate from hydrogen release from a solid solution in the matrix of LiBH4 low temperature phase. The exotherm activation energy has been measured to be 100 kJ mol–1. Calorimetric measurements under argon and hydrogen have shown that for the milled sample, the endothermic peak of the LT → HT transition is split in two when the PDSC scan is performed under hydrogen atmosphere. Synchrotron X-ray powder diffraction on the milled LiBH4 sample revealed only a single-step transition from the LT to HT phase, both under vacuum and under 2 and 40 bar of hydrogen pressure. The axial ratios for the LT LiBH4 below 300 K are significantly altered by milling; they are also considerably different under 40 bar of hydrogen, indicating an interaction between the hydrogen gas and the LT LiBH4 solid phase. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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Review

Jump to: Research

3045 KiB  
Review
Electrochemical and Optical Properties of Magnesium-Alloy Hydrides Reviewed
by Thirugnasambandam G. Manivasagam, Kamil Kiraz and Peter H. L. Notten
Crystals 2012, 2(4), 1410-1433; https://doi.org/10.3390/cryst2041410 - 15 Oct 2012
Cited by 21 | Viewed by 8968
Abstract
As potential hydrogen storage media, magnesium based hydrides have been systematically studied in order to improve reversibility, storage capacity, kinetics and thermodynamics. The present article deals with the electrochemical and optical properties of Mg alloy hydrides. Electrochemical hydrogenation, compared to conventional gas phase [...] Read more.
As potential hydrogen storage media, magnesium based hydrides have been systematically studied in order to improve reversibility, storage capacity, kinetics and thermodynamics. The present article deals with the electrochemical and optical properties of Mg alloy hydrides. Electrochemical hydrogenation, compared to conventional gas phase hydrogen loading, provides precise control with only moderate reaction conditions. Interestingly, the alloy composition determines the crystallographic nature of the metal-hydride: a structural change is induced from rutile to fluorite at 80 at.% of Mg in Mg-TM alloy, with ensuing improved hydrogen mobility and storage capacity. So far, 6 wt.% (equivalent to 1600 mAh/g) of reversibly stored hydrogen in MgyTM(1-y)Hx (TM: Sc, Ti) has been reported. Thin film forms of these metal-hydrides reveal interesting electrochromic properties as a function of hydrogen content. Optical switching occurs during (de)hydrogenation between the reflective metal and the transparent metal hydride states. The chronological sequence of the optical improvements in optically active metal hydrides starts with the rare earth systems (YHx), followed by Mg rare earth alloy hydrides (MgyGd(1-y)Hx) and concludes with Mg transition metal hydrides (MgyTM(1-y)Hx). In-situ optical characterization of gradient thin films during (de)hydrogenation, denoted as hydrogenography, enables the monitoring of alloy composition gradients simultaneously. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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2835 KiB  
Review
Electronic Principles of Hydrogen Incorporation and Dynamics in Metal Hydrides
by Nenad Ivanović, Nikola Novaković, Ivana Radisavljević, Ljiljana Matović and Jasmina Grbović Novaković
Crystals 2012, 2(3), 1261-1282; https://doi.org/10.3390/cryst2031261 - 30 Aug 2012
Cited by 2 | Viewed by 9833
Abstract
An approach to various metal hydrides based on electronic principles is presented. The effective medium theory (EMT) is used to illustrate fundamental aspects of metal-hydrogen interaction and clarify the most important processes taking place during the interaction. The elaboration is extended using the [...] Read more.
An approach to various metal hydrides based on electronic principles is presented. The effective medium theory (EMT) is used to illustrate fundamental aspects of metal-hydrogen interaction and clarify the most important processes taking place during the interaction. The elaboration is extended using the numerous existing results of experiment and calculations, as well as using some new material. In particular, the absorption/desorption of H in the Mg/MgH2 system is analyzed in detail, and all relevant initial structures and processes explained. Reasons for the high stability and slow sorption in this system are noted, and possible solutions proposed. The role of the transition-metal impurities in MgH2 is briefly discussed, and some interesting phenomena, observed in complex intermetallic compounds, are mentioned. The principle mechanism governing the Li-amide/imide transformation is also discussed. Latterly, some perspectives for the metal-hydrides investigation from the electronic point of view are elucidated. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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1437 KiB  
Review
Moderate Temperature Dense Phase Hydrogen Storage Materials within the US Department of Energy (DOE) H2 Storage Program: Trends toward Future Development
by Scott McWhorter, Kathleen O’Malley, Jesse Adams, Grace Ordaz, Katie Randolph and Ned T. Stetson
Crystals 2012, 2(2), 413-445; https://doi.org/10.3390/cryst2020413 - 10 May 2012
Cited by 12 | Viewed by 11365
Abstract
Hydrogen has many positive attributes that make it a viable choice to augment the current portfolio of combustion-based fuels, especially when considering reducing pollution and greenhouse gas (GHG) emissions. However, conventional methods of storing H2 via high-pressure or liquid H2 do [...] Read more.
Hydrogen has many positive attributes that make it a viable choice to augment the current portfolio of combustion-based fuels, especially when considering reducing pollution and greenhouse gas (GHG) emissions. However, conventional methods of storing H2 via high-pressure or liquid H2 do not provide long-term economic solutions for many applications, especially emerging applications such as man-portable or stationary power. Hydrogen storage in materials has the potential to meet the performance and cost demands, however, further developments are needed to address the thermodynamics and kinetics of H2 uptake and release. Therefore, the US Department of Energy (DOE) initiated three Centers of Excellence focused on developing H2 storage materials that could meet the stringent performance requirements for on-board vehicular applications. In this review, we have summarized the developments that occurred as a result of the efforts of the Metal Hydride and Chemical Hydrogen Storage Centers of Excellence on materials that bind hydrogen through ionic and covalent linkages and thus could provide moderate temperature, dense phase H2 storage options for a wide range of emerging Proton Exchange Membrane Fuel Cell (PEM FC) applications. Full article
(This article belongs to the Special Issue Hydrogen Storage Alloys)
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