Rare Earth Borohydrides—Crystal Structures and Thermal Properties

Rare earth (RE) borohydrides have received considerable attention during the past ten years as possible hydrogen storage materials due to their relatively high gravimetric hydrogen density. This review illustrates the rich chemistry, structural diversity and thermal properties of borohydrides containing RE elements. In addition, it highlights the decomposition and rehydrogenation properties of composites containing RE-borohydrides, light-weight metal borohydrides such as LiBH4 and additives such as LiH

Deuterium Exchange Dynamics in Zr_2NiD_(4.8) Studied by ^2H MAS NMR Spectroscopy

Variable temperature (VT) ^2H magic angle spinning (MAS) spectroscopy was employed to measure deuterium diffusion behavior in the Zr_2NiD_(4.8) phase. ^2H MAS NMR spectrum at ∼190 K provides with well-resolved 4 different site occupancies which can be assigned based on the crystal structure (16k (Zr_2Ni_2), 32m (Zr_3Ni), Zr_4 (16/ and 4b)). As the temperature rises, the ^2H peaks sensitively reflect the exchange behavior among the sites with evident change at around 230 K and reaching a uniform distribution of site occupancies, indistinguishable in NMR timescale, above 245 K. This behavior is reflected by the collapse of the ^2H MAS spectrum into a single peak. From analyses of VT MAS NMR spectra, we were able to extract multiple hopping rates and activation energies among face sharing interstices: for example, 32m ↔ 16/ hopping shows _(τc)=2.8×10^(-4)s at 245 K and E_a = 62.2 kJ/mol

Defect chemistry of mixed conducting double Perovskites

Barium Gadolinium Lanthanum Cobaltites with the general formula Ba1-xGd0.8-yLa0.2+x+yCo2O6-δ (BGLC) are reported as Mixed Proton and Electron Conducting materials (MPECs), and have been utilized as positrode (positive electrode) materials for Proton Ceramic Electrochemical Cells (PCECs) [1]. A defect chemical model, treating various charge carrying defects in BGLC was published in 2017 [2] and in this work we expand the model to also comprise formation of protons in BGLC. Protons can be incorporated by two different reactions, in a ratio depending on measurement conditions and the oxidation state of the material. Low temperatures and high pO2 leaves BGLC oxidized, and with increasing electron hole concentration, the hydrogenation reaction is promoted with respect to hydration. Hydrogenation is confirmed by use of isothermal Dry-H2O-D2O switches in thermogravimetric measurements, revealing a larger concentration of protons than expected from hydration only (Figure 1, left). The reduction of BGLC by hydrogenation is slowly counteracted by oxygen uptake combined with an expected cation reordering, bringing the material back to its initial oxidation state after equilibration in wet conditions. By combining oxidation and hydration thermodynamics, hydrogenation entropy and enthalpy can be obtained, making it possible to model proton concentrations from hydration and hydrogenation separately by use of advanced defect chemistry (Figure 1, right). Hydration is proposed to be facilitated by a minor concentration of oxygen vacancies in the O-Co-O layers, where acidic vacancies may accommodate basic hydroxyl groups. These vacancies are neighboured by more basic oxide ions in the O-Ba-O and O-Ln-O layers which in turn may accommodate protons. Please click Additional Files below to see the full abstract

In-situ neutron diffraction during reversible deuterium loading in Ti-rich and Mn-substituted Ti(Fe,Mn)0.90 alloys

Hydrogen is an efficient energy carrier that can be produced from renewable sources, enabling the transition towards CO2-free energy. Hydrogen can be stored for a long period in the solid-state, with suitable alloys. Ti-rich TiFe0.90 compound exhibits a mild activation process for the first hydrogenation, and Ti (Fe,Mn)0.90 substituted alloys can lead to the fine tuning of equilibrium pressure as a function of the final application. In this study, the crystal structure of TiFe(0.90-x)Mnx alloys (x = 0, 0.05 and 0.10) and their deuterides has been determined by in-situ neutron diffraction, while recording Pressure-Composition Isotherms at room temperature. The investigation aims at analysing the influence of Mn for Fe substitution in Ti-rich Ti(Fe,Mn)0.90 alloys on structural properties during reversible deuterium loading, which is still unsolved and seldom explored. After activation, samples have been transferred into custom-made stainlesssteel and aluminium alloy cells used for in-situ neutron diffraction experiments during deuterium loading at ILL and ISIS neutron facilities, respectively. The study enables remarkable understanding on hydrogen storage, basic structural knowledge, and support to the industrial application of TiFe-type alloys for integrated hydrogen tank in energy storage systems by determining the volume expansion during deuteration. Furthermore, the study demonstrates that different contents of Mn do not significantly change the volumetric expansion during phase transitions, affecting only the deuterium content for the gamma phase and the cell evolution for the beta phase. The study confirms that the deuterated structures of the gamma phase upon absorption, beta and ' phase upon desorption, correspond to S.G. Cmmm, P2221 and Pm-3m, respectively.(c) 2022 Elsevier B.V. All rights reserved

The role of anionic processes in Li1−xNi0.44Mn1.56O4 studied by resonant inelastic X-ray scattering

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KNH2 - KH: a metal amide - hydride solid solution

We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2 - ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.Fil: Santoru, Antonio. Helmholtz-zentrum Geesthacht; Alemania. Università di Torino; ItaliaFil: Pistidda, Claudio. Helmholtz-zentrum Geesthacht; AlemaniaFil: Sørby, Magnus H.. Institute for Energy Technology. Physics Department; NoruegaFil: Chierotti, Michele R.. Università di Torino; ItaliaFil: Garroni, Sebastian. University of Sassari; ItaliaFil: Pinatel, Eugenio. Università di Torino; ItaliaFil: Karimi, Fahim. Helmholtz-zentrum Geesthacht; AlemaniaFil: Cao, Hujun. Helmholtz-zentrum Geesthacht; AlemaniaFil: Bergemann, Nils. Helmholtz-zentrum Geesthacht; AlemaniaFil: Le, Thi T.. Helmholtz-zentrum Geesthacht; AlemaniaFil: Puszkiel, Julián Atilio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; ArgentinaFil: Gobetto, Roberto. Università di Torino; ItaliaFil: Baricco, Marcello. Università di Torino; ItaliaFil: Hauback, Bjorn C.. Institute for Energy Technology. Physics Department; NoruegaFil: Klassen, Thomas. Helmholtz-zentrum Geesthacht; AlemaniaFil: Dornheim, Martín. Helmholtz-zentrum Geesthacht; Alemani