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Nanostructured Metal Hydrides for Hydrogen Storage Studied by In Situ Synchrotron and Neutron Diffraction

Published online by Cambridge University Press:  01 February 2011


Volodymyr Yartys
Affiliation:
volodymyr.yartys@ife.no, Institute for Energy Technology, Kjeller, Norway
Roman Denys
Affiliation:
roden74@mail.ru, Institute for Energy Technology, Kjeller, Norway
Jan Petter Maehlen
Affiliation:
jepe@ife.no, Institute for Energy Technology, Kjeller, Norway
Colin J Webb
Affiliation:
j.webb@griffith.edu.au, Griffith University, Queensland Micro- and Nanotechnology Centre, Nathan, Australia
Evan MacA Gray
Affiliation:
e.gray@griffith.edu.au, Griffith University, Queensland Micro- and Nanotechnology Centre, Nathan, Australia
Tomas Blach
Affiliation:
T.Blach@iinet.net.au, Griffith University, Queensland Micro- and Nanotechnology Centre, Nathan, Queensland, Australia
Andrey A. Poletaev
Affiliation:
andrey.poletaev@ife.no, Institute for Energy Technology, Kjeller, Norway
Jan Ketil Solberg
Affiliation:
jan.solberg@material.ntnu.no, Norwegian University of Science and Technology, Trondheim, Norway
Olivier Isnard
Affiliation:
olivier.isnard@grenoble.cnrs.fr, Institute Néel, CNRS/UJF, Grenoble, France

Abstract

This work was focused on studies of the metal hydride materials having a potential in building hydrogen storage systems with high gravimetric and volumetric efficiencies of H storage and formed / decomposed with high rates of hydrogen exchange. In situ diffraction studies of the metal-hydrogen systems were explored as a valuable tool in probing both the mechanism of the phase-structural transformations and their kinetics. Two complementary techniques, namely Neutron Powder Diffraction (NPD) and Synchrotron X-ray diffraction (SR XRD) were utilised. High pressure in situ NPD studies were performed at D2 pressures reaching 1000 bar at the D1B diffractometer accommodated at Institute Laue Langevin, Grenoble. The data of the time resolved in situ SR XRD were collected at the Swiss Norwegian Beam Lines, ESRF, Grenoble in the pressure range up to 50 bar H2 at temperatures 20-400°C.

The systems studied by NPD at high pressures included deuterated Al-modified Laves-type C15 ZrFe2-xAlx intermetallics with x = 0.02; 0.04 and 0.20 and the CeNi5-D2 system. D content, hysteresis of H uptake and release, unit cell expansion and stability of the hydrides systematically change with Al content.

Deuteration exhibited a very fast kinetics; it resulted in increase of the unit cells volumes reaching 23.5 % for ZrFe1.98Al0.02D2.9(1) and associated with exclusive occupancy of the Zr2(Fe,Al)2 tetrahedra.

For CeNi5 deuteration yielded a hexahydride CeNi5D6.2 (20°C, 776 bar D2) and was accompanied by a nearly isotropic volume expansion reaching 30.1% (∆a/a=10.0%; ∆c/c=7.5%). Deuterium atoms fill three different interstitial sites including Ce2Ni2, Ce2Ni3 and Ni4. Significant hysteresis was observed on the first absorption-desorption cycle. This hysteresis decreased on the absorption-desorption cycling.

A different approach to the development of H storage systems is based on the hydrides of light elements, first of all the Mg-based ones. These systems were studied by SR XRD. Reactive ball milling in hydrogen (HRBM) allowed synthesis of the nanostructured Mg-based hydrides.

The experimental parameters (PH2, T, energy of milling, ball / sample ratio and balls size), significantly influence rate of hydrogenation. The studies confirmed (a) a completeness of hydrogenation of Mg into MgH2; (b) indicated a partial transformation of the originally formed -MgH2 into a metastable -MgH2 (a ratio / was 3/1); (c) yielded the crystallite size for the main hydrogenation product, -MgH2, as close to 10 nm. Influence of the additives to Mg on the structure and hydrogen absorption/desorption properties and cycle behaviour of the composites was established and will be discussed in the paper.


Type
Research Article
Copyright
Copyright © Materials Research Society 2010

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References

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