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Advances in Hydrogen Storage Materials Research
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Advances in Hydrogen Storage Materials Research

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: closed (30 April 2019) | Viewed by 27733

Special Issue Editors

Prof. Dr. Takayuki Ichikawa

E-Mail Website
Guest Editor
Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527, Japan
Interests: hydrogen storage; inorganic hydrides; ammonia; ammonolysis; electrolysis; magnesium hydride; amide-imide; chemical compressor
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Ankur Jain

E-Mail Website
Guest Editor
1. Centre for Renewable Energy & Storage, Suresh Gyan Vihar University, Jaipur 302017, India
2. Natural Science Centre for Basic Research and Development, Hiroshima University, Higashi-Hiroshima 739-8530, Japan
Interests: hydrogen energy; hydrogen storage materials; metal hydrides; complex hydrides; lithium ion battery
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Since the 1970s, hydrogen-absorbing alloys, such as AB5, AB2, AB, and so on, have been in focus as hydrogen storage materials in order to realize high volumetric and gravimetric hydrogen media. These alloys, which have difficulty in achieving high gravimetric density of hydrogen, in principle, are not adopted as tank materials for hydrogen-fuel-cell vehicles which have been recently produced. However, inorganic hydrogen storage materials, such as alanate, amide-imide, borohydride, and ammonia borane, which came into use around 2000, and liquid hydrogen storage, such as organic hydrides, annmonia, and formic acid, are being actively researched and developed. Furthermore, it is noteworthy that the development of analytical techniques, such as synchrotron, neutron, TEM, NMR, and XPS, using large facilities, have been especially promoted for research on hydrogen storage materials. This Special Issue is focusing on recent developments towards a higher capacity and higher functionality of such hydrogen storage materials. In addition, we would also pay attention to new analytical methods for materials containing hydrogen. The Guest Editor wishes to receive many interesting and inspiring research papers on these topics.

Prof. Dr. Takayuki Ichikawa
Prof. Dr. Ankur Jain
Guest Editor

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Keywords

  • Hydrides with High Gravimetric Capacity
  • Hydrides with New Function
  • Hydrogen Storage Alloys
  • Inorganic Hydrides
  • Organic Hydrides
  • Hydrogen Adsorption Materials
  • Composite Materials for Hydrogen Storage
  • Novel Analytical Techniques for Hydrogen Storage Materials
  • Novel Computational Techniques for Hydrogen Storage Materials

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Published Papers (8 papers)

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Research

10 pages, 2094 KiB  
Article
Suitability Evaluation of LaNi5 as Hydrogen-Storage-Alloy Actuator by In-Situ Displacement Measurement during Hydrogen Pressure Change
by Kenta Goto, Tomoyuki Hirata, Isao Yamamoto and Wataru Nakao
Molecules 2019, 24(13), 2420; https://doi.org/10.3390/molecules24132420 - 1 Jul 2019
Cited by 19 | Viewed by 3209
Abstract
The swelling ability of LaNi5 for application to hydrogen-storage-alloy (HSA) actuator is discussed through the measurement of the swelling ratio in hydrogen. The HSA actuator is driven by hydrogen pressure change causing the swelling of HSA. LaNi5 is one of the [...] Read more.
The swelling ability of LaNi5 for application to hydrogen-storage-alloy (HSA) actuator is discussed through the measurement of the swelling ratio in hydrogen. The HSA actuator is driven by hydrogen pressure change causing the swelling of HSA. LaNi5 is one of the candidate materials for HSA actuators as well as palladium. Some prototypes of HSA actuators using LaNi5 have been fabricated; however, the kinetic swelling ability of LaNi5 itself has been not investigated. In this paper, the authors investigated the static and kinetic swelling ability of LaNi5 powder under hydrogen atmosphere. The results showed that the swelling ratio increased by 0.12 at the phase transition pressure. Response time decreased with an increase in the charged pressure during absorption, while it remained constant during discharge. Reaction kinetics revealed that these swelling behaviors were explained by hydrogen absorption and lattice expansion. The swelling ability of LaNi5 was also compared with that of palladium. The results show that LaNi5 swells 1.8 times more than palladium under 0.5 MPa. LaNi5 is suitable for an actuator driven repeatedly under more than the phase transition pressure. Palladium can be used for one-way-operation actuator even under 0.1 MPa since its response time during the evacuation was much longer than during the pressurization. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials Research)
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15 pages, 7069 KiB  
Article
Scandium Decoration of Boron Doped Porous Graphene for High-Capacity Hydrogen Storage
by Jing Wang, Yuhong Chen, Lihua Yuan, Meiling Zhang and Cairong Zhang
Molecules 2019, 24(13), 2382; https://doi.org/10.3390/molecules24132382 - 27 Jun 2019
Cited by 37 | Viewed by 3248
Abstract
The hydrogen storage properties of the Scandium (Sc) atom modified Boron (B) doped porous graphene (PG) system were studied based on the density functional theory (DFT). For a single Sc atom, the most stable adsorption position on B-PG is the boron-carbon hexagon center [...] Read more.
The hydrogen storage properties of the Scandium (Sc) atom modified Boron (B) doped porous graphene (PG) system were studied based on the density functional theory (DFT). For a single Sc atom, the most stable adsorption position on B-PG is the boron-carbon hexagon center after doping with the B atom. The corresponding adsorption energy of Sc atoms was −4.004 eV. Meanwhile, five H2 molecules could be adsorbed around a Sc atom with the average adsorption energy of −0.515 eV/H2. Analyzing the density of states (DOS) and the charge population of the system, the adsorption of H2 molecules in Sc-B/PG system is mainly attributed to an orbital interaction between H and Sc atoms. For the H2 adsorption, the Coulomb attraction between H2 molecules (negatively charged) and Sc atoms (positively charged) also played a critical role. The largest hydrogen storage capacity structure was two Sc atoms located at two sides of the boron-carbon hexagon center in the Sc-B/PG system. Notably, the theoretical hydrogen storage capacity was 9.13 wt.% with an average adsorption energy of −0.225 eV/H2. B doped PG prevents the Sc atom aggregating and improves the hydrogen storage effectively because it can increase the adsorption energy of the Sc atom and H2 molecule. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials Research)
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11 pages, 3394 KiB  
Article
Hydrogen Desorption Properties of LiBH4/xLiAlH4 (x = 0.5, 1, 2) Composites
by Qing He, Dongdong Zhu, Xiaocheng Wu, Duo Dong, Meng Xu and Zhaofei Tong
Molecules 2019, 24(10), 1861; https://doi.org/10.3390/molecules24101861 - 15 May 2019
Cited by 13 | Viewed by 2693
Abstract
A detailed analysis of the dehydrogenation mechanism of LiBH4/xLiAlH4 (x = 0.5, 1, 2) composites was performed by thermogravimetry (TG), differential scanning calorimetry (DSC), mass spectral analysis (MS), powder X-ray diffraction (XRD) and scanning electronic microscopy (SEM), [...] Read more.
A detailed analysis of the dehydrogenation mechanism of LiBH4/xLiAlH4 (x = 0.5, 1, 2) composites was performed by thermogravimetry (TG), differential scanning calorimetry (DSC), mass spectral analysis (MS), powder X-ray diffraction (XRD) and scanning electronic microscopy (SEM), along with kinetic investigations using a Sievert-type apparatus. The results show that the dehydrogenation pathway of LiBH4/xLiAlH4 had a four-step character. The experimental dehydrogenation amount did not reach the theoretical expectations, because the products such as AlB2 and LiAl formed a passivation layer on the surface of Al and the dehydrogenation reactions associated with Al could not be sufficiently carried out. Kinetic investigations discovered a nonlinear relationship between the activation energy (Ea) of dehydrogenation reactions associated with Al and the ratio x, indicating that the Ea was determined both by the concentration of Al produced by the decomposition of LiAlH4 and the amount of free surface of it. Therefore, the amount of effective contact surface of Al is the rate-determining factor for the overall dehydrogenation of the LiBH4/xLiAlH4 composites. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials Research)
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8 pages, 2068 KiB  
Article
Activation and Disproportionation of Zr2Fe Alloy as Hydrogen Storage Material
by Jiangfeng Song, Jingchuan Wang, Xiaoyu Hu, Daqiao Meng and Shumao Wang
Molecules 2019, 24(8), 1542; https://doi.org/10.3390/molecules24081542 - 19 Apr 2019
Cited by 12 | Viewed by 2910
Abstract
As a hydrogen storage material, Zr2Fe alloy has many advantages such as fast hydrogen absorption speed, high tritium recovery efficiency, strong anti-pulverization ability, and difficulty self-igniting in air. Zr2Fe alloy has lower hydrogen absorption pressure at room temperature than [...] Read more.
As a hydrogen storage material, Zr2Fe alloy has many advantages such as fast hydrogen absorption speed, high tritium recovery efficiency, strong anti-pulverization ability, and difficulty self-igniting in air. Zr2Fe alloy has lower hydrogen absorption pressure at room temperature than LaNi5 alloy. Compared with the ZrVFe alloy, the hydrogen release temperature of Zr2Fe is lower so that the material can recover hydrogen isotopes at lower hydrogen concentration efficiently. Unfortunately, the main problem of Zr2Fe alloy in application is that a disproportionation reaction is easy to occur after hydrogen absorption at high temperature. At present, there is little research on the generation and influencing factors of a disproportionation reaction in Zr2Fe alloy. In this paper, the effects of temperature and hydrogen pressure on the disproportionation of Zr2Fe alloy were studied systematically. The specific activation conditions and experimental parameters for reducing alloy disproportionation are given, which provide a reference for the specific application of Zr2Fe alloy. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials Research)
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10 pages, 1126 KiB  
Article
Eutectic Phenomenon of LiNH2-KH Composite in MH-NH3 Hydrogen Storage System
by Kiyotaka Goshome, Ankur Jain, Hiroki Miyaoka, Hikaru Yamamoto, Yoshitsugu Kojima and Takayuki Ichikawa
Molecules 2019, 24(7), 1348; https://doi.org/10.3390/molecules24071348 - 5 Apr 2019
Cited by 5 | Viewed by 3330
Abstract
Hydrogenation of a lithium-potassium (double-cation) amide (LiK(NH2)2), which is generated as a product by ammonolysis of litium hydride and potassium hydride (LiH-KH) composite, is investigated in details. As a result, lithium amide (LiNH2) and KH are generated [...] Read more.
Hydrogenation of a lithium-potassium (double-cation) amide (LiK(NH2)2), which is generated as a product by ammonolysis of litium hydride and potassium hydride (LiH-KH) composite, is investigated in details. As a result, lithium amide (LiNH2) and KH are generated after hydrogenation at 160 °C as an intermediate. It is noteworthy that the mixture of LiH and KNH2 has a much lower melting point than that of the individual melting points of LiNH2 and KH, which is recognized as a eutectic phenomenon. The hydrogenation temperature of LiNH2 in the mixture is found to be significantly lower than that of LiNH2 itself. This improvement of reactivity must be due to kinetic modification, induced by the enhanced atomic mobility due to the eutectic interaction. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials Research)
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9 pages, 1630 KiB  
Article
Ti-V-C-Based Alloy with a FCC Lattice Structure for Hydrogen Storage
by Bo Li, Liqing He, Jianding Li, Hai-Wen Li, Zhouguang Lu and Huaiyu Shao
Molecules 2019, 24(3), 552; https://doi.org/10.3390/molecules24030552 - 2 Feb 2019
Cited by 2 | Viewed by 3810
Abstract
Here we report a Ti50V50-10 wt.% C alloy with a unique lattice and microstructure for hydrogen storage development. Different from a traditionally synthesized Ti50V50 alloy prepared by a melting method and having a body-centered cubic (BCC) [...] Read more.
Here we report a Ti50V50-10 wt.% C alloy with a unique lattice and microstructure for hydrogen storage development. Different from a traditionally synthesized Ti50V50 alloy prepared by a melting method and having a body-centered cubic (BCC) structure, this Ti50V50-C alloy synthesized by a mechanical alloying method is with a face-centered cubic (FCC) structure (space group: Fm-3m No. 225). The crystalline size is 60 nm. This alloy may directly absorb hydrogen near room temperature without any activation process. Mechanisms of the good kinetics from lattice and microstructure aspects were discussed. Findings reported here may indicate a new possibility in the development of future hydrogen storage materials. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials Research)
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32 pages, 21310 KiB  
Article
Microstructure Optimization of Mg-Alloys by the ECAP Process Including Numerical Simulation, SPD Treatments, Characterization, and Hydrogen Sorption Properties
by Nataliya Skryabina, Valery Aptukov, Petr Romanov, Daniel Fruchart, Patricia De Rango, Gregory Girard, Carlos Grandini, Hugo Sandim, Jacques Huot, Julien Lang, Rosario Cantelli and Fabrice Leardini
Molecules 2019, 24(1), 89; https://doi.org/10.3390/molecules24010089 - 27 Dec 2018
Cited by 23 | Viewed by 4428
Abstract
Both numerical simulation and hardness measurements were used to determine the mechanical and microstructural behavior of AZ31 bulk samples when submitted to the Equal Channel Angular Pressing (ECAP) technique. Billets of this representative of Mg-rich alloys were submitted to different numbers of passes [...] Read more.
Both numerical simulation and hardness measurements were used to determine the mechanical and microstructural behavior of AZ31 bulk samples when submitted to the Equal Channel Angular Pressing (ECAP) technique. Billets of this representative of Mg-rich alloys were submitted to different numbers of passes for various ECAP modes (anisotropic A, isotropic BC). The strain distribution, the grain size refinement, and the micro-hardness were used as indicators to quantify the effectiveness of the different processing routes. Structural characterizations at different scales were achieved using Scanning Electron Microscopy (SEM), micro-analysis, metallography, Small Angle Neutron Scattering SANS, X-Ray Diffraction (XRD), and texture determination. The grain and crystallite size distribution and orientation as well as defect impacts were determined. Anelastic Spectroscopy (AS) on mechanically deformed samples have shown that the temperature of ECAP differentiate the fragile to ductile regime. MgH2 consolidated powders were checked for using AS to detect potential hydrogen motions and interaction with host metal atoms. After further optimization, the different mechanically-treated samples were submitted to hydrogenation/dehydrogenation (H/D) cycles, which shows that, for a few passes, the BC mode is better than the A one, as supported by theoretical and experimental microstructure analyses. Accordingly, the hydrogen uptake and (H/D) reactions were correlated with the optimized microstructure peculiarities and interpreted in terms of Johnson-Avrami- Mehl-Kolmogorov (JAMK) and Jander models, successively. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials Research)
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8 pages, 2683 KiB  
Article
Improvement of Hydrogen Desorption Characteristics of MgH2 With Core-shell Ni@C Composites
by Cuihua An and Qibo Deng
Molecules 2018, 23(12), 3113; https://doi.org/10.3390/molecules23123113 - 28 Nov 2018
Cited by 17 | Viewed by 3575
Abstract
Magnesium hydride (MgH2) has become popular to study in hydrogen storage materials research due to its high theoretical capacity and low cost. However, the high hydrogen desorption temperature and enthalpy as well as the depressed kinetics, have severely blocked its actual [...] Read more.
Magnesium hydride (MgH2) has become popular to study in hydrogen storage materials research due to its high theoretical capacity and low cost. However, the high hydrogen desorption temperature and enthalpy as well as the depressed kinetics, have severely blocked its actual utilizations. Hence, our work introduced Ni@C materials with a core-shell structure to synthesize MgH2-x wt.% Ni@C composites for improving the hydrogen desorption characteristics. The influences of the Ni@C addition on the hydrogen desorption performances and micro-structure of MgH2 have been well investigated. The addition of Ni@C can effectively improve the dehydrogenation kinetics. It is interesting found that: i) the hydrogen desorption kinetics of MgH2 were enhanced with the increased Ni@C additive amount; and ii) the dehydrogenation amount decreased with a rather larger Ni@C additive amount. The additive amount of 4 wt.% Ni@C has been chosen in this study for a balance of kinetics and amount. The MgH2-4 wt.% Ni@C composites release 5.9 wt.% of hydrogen in 5 min and 6.6 wt.% of hydrogen in 20 min. It reflects that the enhanced hydrogen desorption is much faster than the pure MgH2 materials (0.3 wt.% hydrogen in 20 min). More significantly, the activation energy (EA) of the MgH2-4 wt.% Ni@C composites is 112 kJ mol−1, implying excellent dehydrogenation kinetics. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials Research)
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