Designing an Ab2-type alloy (TIZr-CrMNMO) for the hybrid hydrogen storage concept

The hybrid hydrogen storage method consists of the combination of both solid-state metal hydrides and gas hydrogen storage. This method is regarded as a promising trade-off solution between the already developed high-pressure storage reservoir, utilized in the automobile industry, and solid-state storage through the formation of metal hydrides. Therefore, it is possible to lower the hydrogen pressure and to increase the hydrogen volumetric density. In this work, we design a non-stoichiometric AB2 C14-Laves alloy composed of (Ti0.9Zr0.1)1.25Cr0.85Mn1.1Mo0.05. This alloy is synthesized by arc-melting, and the thermodynamic and kinetic behaviors are evaluated in a high-pressure Sieverts apparatus. Proper thermodynamic parameters are obtained in the range of temperature and pressure from 3 to 85 ◦C and from 15 to 500 bar: ∆Habs. = 22 ± 1 kJ/mol H2, ∆Sabs. = 107 ± 2 J/K mol H2, and ∆Hdes. = 24 ± 1 kJ/mol H2, ∆Sdes. = 110 ± 3 J/K mol H2. The addition of 10 wt.% of expanded natural graphite (ENG) allows the improvement of the heat transfer properties, showing a reversible capacity of about 1.5 wt.%, cycling stability and hydrogenation/dehydrogenation times between 25 to 70 s. The feasibility for the utilization of the designed material in a high-pressure tank is also evaluated, considering practical design parameters.Fil: Puszkiel, Julián Atilio. Helmholtz-zentrum Geesthacht; Alemania. Instituto de Investigaciones Energéticas de Cataluña; España. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada CAB. Departamento Fisicoquímica de Materiales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; ArgentinaFil: Bellosta von Colbe, José M.. Helmholtz-zentrum Geesthacht; AlemaniaFil: Jepsen, Julian. Helmholtz-zentrum Geesthacht; Alemania. Helmut Schmidt University; AlemaniaFil: Mitrokhin, Sergey V.. Lomonosov Moscow State University; RusiaFil: Movlaev, Elshad. Lomonosov Moscow State University; RusiaFil: Verbetsky, Victor. Lomonosov Moscow State University; RusiaFil: Klassen, Thomas. Helmholtz-zentrum Geesthacht; Alemania. Helmut Schmidt University; Alemani

Fundamental material properties of the 2LiBH4-MgH2 reactive hydride composite for hydrogen storage: (I) Thermodynamic and heat transfer properties

Thermodynamic and heat transfer properties of the 2LiBH4-MgH2 composite (Li-RHC) system are experimentally determined and studied as a basis for the design and development of hydrogen storage tanks. Besides the determination and discussion of the properties, different measurement methods are applied and compared to each other. Regarding thermodynamics, reaction enthalpy and entropy are determined by pressure-concentration-isotherms and coupled manometric-calorimetric measurements. For thermal diffusivity calculation, the specific heat capacity is measured by high-pressure differential scanning calorimetry and the effective thermal conductivity is determined by the transient plane source technique and in situ thermocell. Based on the results obtained from the thermodynamics and the assessment of the heat transfer properties, the reaction mechanism of the Li-RHC and the issues related to the scale-up for larger hydrogen storage systems are discussed in detail.Fil: Jepsen, Julian. Helmholtz-Zentrum Geesthacht; AlemaniaFil: Milanese, Chiara. University of Pavia; ItaliaFil: Puszkiel, Julián Atilio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Helmholtz-Zentrum Geesthacht; AlemaniaFil: Girella, Alessandro. University of Pavia; ItaliaFil: Schiavo, Benedetto. Universidad de Palermo; Argentina. Istituto per le Tecnologie Avanzate; ItaliaFil: Lozano, Gustavo A.. Helmholtz-Zentrum Geesthacht; Alemania. BASF; AlemaniaFil: Capurso, Giovanni. Helmholtz-Zentrum Geesthacht; AlemaniaFil: Von Colbe, José M. Bellosta. Helmholtz-Zentrum Geesthacht; AlemaniaFil: Marini, Amedeo. University of Pavia; ItaliaFil: Kabelac, Stephan. Leibniz Universität Hannover; AlemaniaFil: Dornheim, Martin. Helmholtz-Zentrum Geesthacht; AlemaniaFil: Klassen, Thomas. Helmholtz-Zentrum Geesthacht; Alemani

Fundamental material properties of the 2LiBH4-MgH2 reactive hydride composite for hydrogen storage: (II) Kinetic properties

Reaction kinetic behaviour and cycling stability of the 2LiBH4-MgH2 reactive hydride composite (Li-RHC) are experimentally determined and analysed as a basis for the design and development of hydrogen storage tanks. In addition to the determination and discussion about the properties; different measurement methods are applied and compared. The activation energies for both hydrogenation and dehydrogenation are determined by the Kissinger method and via the fitting of solid-state reaction kinetic models to isothermal volumetric measurements. Furthermore, the hydrogen absorption-desorption cycling stability is assessed by titration measurements. Finally, the kinetic behaviour and the reversible hydrogen storage capacity of the Li-RHC are discussed.Fil: Jepsen, Julian. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; AlemaniaFil: Milanese, Chiara. Università degli Studi di Pavia; ItaliaFil: Puszkiel, Julián Atilio. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; ArgentinaFil: Girella, Alessandro. Università degli Studi di Pavia; ItaliaFil: Schiavo, Benedetto. Università degli Studi di Palermo; ItaliaFil: Lozano, Gustavo A.. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; AlemaniaFil: Capurso, Giovanni. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; AlemaniaFil: Von Colbe, José M. Bellosta. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; AlemaniaFil: Marini, Amedeo. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; ArgentinaFil: Kabelac, Stephan. Leibniz Universität Hannover; AlemaniaFil: Dornheim, Martin. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; AlemaniaFil: Klassen, Thomas. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; Alemani

New Insight on the Hydrogen Absorption Evolution of the Mg–Fe–H System under Equilibrium Conditions

Mg2FeH6 is regarded as potential hydrogen and thermochemical storage medium due to its high volumetric hydrogen (150 kg/m3) and energy (0.49 kWh/L) densities. In this work, the mechanism of formation of Mg2FeH6 under equilibrium conditions is thoroughly investigated applying volumetric measurements, X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), and the combination of scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS) and high-resolution transmission electron microscopy (HR-TEM). Starting from a 2Mg:Fe stoichiometric powder ratio, thorough characterizations of samples taken at different states upon hydrogenation under equilibrium conditions confirm that the formation mechanism of Mg2FeH6 occurs from elemental Mg and Fe by columnar nucleation of the complex hydride at boundaries of the Fe seeds. The formation of MgH2 is enhanced by the presence of Fe. However, MgH2 does not take part as intermediate for the formation of Mg2FeH6 and acts as solid-solid diffusion barrier which hinders the complete formation of Mg2FeH6. This work provides novel insight about the formation mechanism of Mg2FeH6

New Insight on the Hydrogen Absorption Evolution of the Mg–Fe–H System under Equilibrium Conditions

Mg₂FeH₆ is regarded as potential hydrogen and thermochemical storage medium due to its high volumetric hydrogen (150 kg/m³) and energy (0.49 kWh/L) densities. In this work, the mechanism of formation of Mg₂FeH₆ under equilibrium conditions is thoroughly investigated applying volumetric measurements, X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), and the combination of scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS) and high-resolution transmission electron microscopy (HR-TEM). Starting from a 2Mg:Fe stoichiometric powder ratio, thorough characterizations of samples taken at different states upon hydrogenation under equilibrium conditions confirm that the formation mechanism of Mg₂FeH6 occurs from elemental Mg and Fe by columnar nucleation of the complex hydride at boundaries of the Fe seeds. The formation of MgH₂ is enhanced by the presence of Fe. However, MgH₂ does not take part as intermediate for the formation of Mg₂FeH₆ and acts as solid-solid diffusion barrier which hinders the complete formation of Mg₂FeH₆. This work provides novel insight about the formation mechanism of Mg₂FeH₆.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

An effective activation method for industrially produced TiFeMn powder for hydrogen storage

This work proposes an effective thermal activation method with low technical effort for industrially produced titanium-iron-manganese powders (TiFeMn) for hydrogen storage. In this context, the influence of temperature and particle size of TiFeMn on the activation process is systematically studied. The results obtained from this investigation suggest that the activation of the TiFeMn material at temperatures as low as 50 °C is already possible, with a combination of “Dynamic” and “Static” routines, and that an increase to 90 °C strongly reduces the incubation time for activation, i.e. the incubation time of the sample with the two routines at 90 °C is about 0.84 h, while ∼ 277 h is required for the sample treated at 50 °C in both “Dynamic” and “Static” sequences. Selecting TiFeMn particles of larger size also leads to significant improvements in the activation performance of the investigated material. The proposed activation routine makes it possible to overcome the oxide layer existing on the compound surface, which acts as a diffusion barrier for the hydrogen atoms. This activation method induces further cracks and defects in the powder granules, generating new surfaces for hydrogen absorption with greater frequency, and thus leading to faster sorption kinetics in the subsequent absorption-desorption cycles

Application of hydrides in hydrogen storage and compression: Achievements, outlook and perspectives

Metal hydrides are known as a potential efficient, low-risk option for high-density hydrogen storage since the late 1970s. In this paper, the present status and the future perspectives of the use of metal hydrides for hydrogen storage are discussed. Since the early 1990s, interstitial metal hydrides are known as base materials for Ni – metal hydride rechargeable batteries. For hydrogen storage, metal hydride systems have been developed in the 2010s [1] for use in emergency or backup power units, i. e. for stationary applications. With the development and completion of the first submarines of the U212 A series by HDW (now Thyssen Krupp Marine Systems) in 2003 and its export class U214 in 2004, the use of metal hydrides for hydrogen storage in mobile applications has been established, with new application fields coming into focus. In the last decades, a huge number of new intermetallic and partially covalent hydrogen absorbing compounds has been identified and partly more, partly less extensively characterized. In addition, based on the thermodynamic properties of metal hydrides, this class of materials gives the opportunity to develop a new hydrogen compression technology. They allow the direct conversion from thermal energy into the compression of hydrogen gas without the need of any moving parts. Such compressors have been developed and are nowadays commercially available for pressures up to 200 bar. Metal hydride based compressors for higher pressures are under development. Moreover, storage systems consisting of the combination of metal hydrides and high-pressure vessels have been proposed as a realistic solution for on-board hydrogen storage on fuel cell vehicles. In the frame of the “Hydrogen Storage Systems for Mobile and Stationary Applications” Group in the International Energy Agency (IEA) Hydrogen Task 32 “Hydrogen-based energy storage”, different compounds have been and will be scaled-up in the near future and tested in the range of 500 g to several hundred kg for use in hydrogen storage applications.Fil: Bellosta von Colbe, Jose. Helmholtz-Zentrum Geesthacht; AlemaniaFil: Ares Fernández, José Ramón. Universidad Autónoma de Madrid; EspañaFil: Jussara, Barale. Università di Torino; ItaliaFil: Baricco, Marcello. Università di Torino; ItaliaFil: Buckley, Craig E.. Curtin University; AustraliaFil: Capurso, Giovanni. Helmholtz Zentrum Geesthacht; AlemaniaFil: Gallandat, Noris. GRZ Technologies Ltd; SuizaFil: Grant, David M.. Science and Technology Facilities Council of Nottingham. Rutherford Appleton Laboratory; Reino Unido. University of Nottingham; Estados UnidosFil: Guzik, Matylda N.. University of Oslo; NoruegaFil: Jacob, Isaac. Ben Gurion University of the Negev; IsraelFil: Jensen, Emil H.. University of Oslo; NoruegaFil: Jensen, Torben. University Aarhus; DinamarcaFil: Jepsen, Julian. Helmholtz Zentrum Geesthacht; AlemaniaFil: Klassen, Thomas. Helmholtz Zentrum Geesthacht; AlemaniaFil: Lototskyy, Mykhaylol V.. University of Cape Town; SudáfricaFil: Manickam, Kandavel. University of Nottingham; Estados Unidos. Science and Technology Facilities Council of Nottingham. Rutherford Appleton Laboratory; Reino UnidoFil: Montone, Amelia. Casaccia Research Centre; ItaliaFil: Puszkiel, Julián Atilio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Helmholtz Zentrum Geesthacht; AlemaniaFil: Sartori, Sabrina. University of Oslo; NoruegaFil: Sheppard, Drew A.. Curtin University; AustraliaFil: Stuart, Alastair. University of Nottingham; Estados Unidos. Science and Technology Facilities Council of Nottingham. Rutherford Appleton Laboratory; Reino UnidoFil: Walker, Gavin. University of Nottingham; Estados Unidos. Science and Technology Facilities Council of Nottingham. Rutherford Appleton Laboratory; Reino UnidoFil: Webb, Colin J.. Griffith University; AustraliaFil: Yang, Heena. Empa Materials Science & Technology; Suiza. École Polytechnique Fédérale de Lausanne; SuizaFil: Yartys, Volodymyr. Institute for Energy Technology; NoruegaFil: Züttel, Andreas. Empa Materials Science & Technology; Suiza. École Polytechnique Fédérale de Lausanne; SuizaFil: Dornheim, Martin. Helmholtz Zentrum Geesthacht; Alemani

Hydrogen storage in light metal hybrides

In dieser Arbeit wurden mehrere Dotierungsverbindungen auf ihre Effektivität in der Katalyse der Natriumalanat De- und Hydrierung getestet. Das Mahlen, wodurch die dotierten Proben entstehen, wurde zu einem kontrollierbaren Prozess über die in situ Messung der Wasserstoffentwicklung. Eine Ein-Schritt Synthese von dotiertem NaAlH$_{4}$ in der Hochdruckkugelmühle wurde entwickelt, was Proben mit verbesserten Eigenschaften lieferte. Eine automatisierte isobarische Zyklisieranlage wurde gebaut und programmiert. Sie erlaubte Langzeits- und Stabilitätsversuche sowie die Feststellung von Reaktionsgeschwindigkeitsmaxima für die Hydrierung bei bestimmte Temperaturen unter konstantem Druck. Die Rolle des Katalysators im Splitten von Wasserstoffmolekülen wurde schliesslich in Isotopenaustausch Experimenten beobachtet. sowie Wasserstoffaustausch zwischen Probe und Atmosphäre unter milden Bedingungen.Several doping substances were tested as to the effectiveness of the catalyst they yielded for the de- and hydrogenation of sodium alanate. The milling process through which the doped samples are synthesized was improved through the addition of a device to measure the hydrogen evolution in situ during milling. A single-step synthesis of doped NaAlH$_{4}$ in a high pressure mill was developed, yielding samples with improved characteristics. An automatic isobaric cycling apparatus was built and programmed, which allowed stability experiments over a long period of time, as well as the identification of hydrogenation rate maxima at two different pressures. Finally, the role of the catalyst in the hydrogen molecule splitting reaction was observed in isotope exchange experiments, as well as hydrogen exchange between the sample bulk and the gas atmosphere under mild conditions

INTEGRATED MATERIAL AND PROCESS FOR INTEGRATED OPERATION OF A HYDRIDE STORAGE SYSTEM

The present invention relates to a composite material for hydrogen storage based on metal hydrides and to a method of operating a hydrogen storage system based on metal hydrides capable of releasing and absorbing hydrogen. Such hydrogen storage systems based on metal hydrides may be applicable as a fuel source for a fuel cell. The composite material for hydrogen storage comprises a powder or pellets of a hydride and a phase changing material (PCM), wherein the PCM is an encapsulated phase changing material (EPCM) which is homogeneously dispersed within the powder or pellets of the hydride