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hal.structure.identifierLaboratory of Crystallography
dc.contributor.authorCERNY, Radovan
hal.structure.identifierLaboratory of Crystallography
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorPENIN, Nicolas
hal.structure.identifierLaboratory of Crystallography
dc.contributor.authorD'ANNA, Vincenza
hal.structure.identifierDepartment of Physical Chemistry
dc.contributor.authorHAGEMANN, Hans
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDURAND, Etienne
hal.structure.identifierDepartment of Inorganic Chemistry
dc.contributor.authorRUZICKA, Jakub
dc.date.issued2011
dc.identifier.issn1359-6454
dc.description.abstractEnA solid solution of magnesium and manganese borohydrides was studied by in situ synchrotron radiation X-ray powder diffraction and infrared spectroscopy. A combination of thermogravimetry, mass and infrared spectroscopy, and atomic emission spectroscopy were applied to clarify the thermal gas desorption of pure Mn(BH<sub>4</sub>)<sub>2</sub> and a solid solution of composition Mg<sub>0.5</sub>Mn<sub>0.5</sub>(BH<sub>4</sub>)<sub>2</sub>. Mg<i><sub>x</sub></i>Mn<sub>(1−</sub><i><sub>x</sub></i><sub>)</sub>(BH<sub>4</sub>)<sub>2</sub> (<i>x = </i>0-0.8) conserves the trigonal structure of Mn(BH<sub>4</sub>)<sub>2</sub> at room temperature. Manganese is dissolved in the hexagonal structure of α-Mg(BH<sub>4</sub>)<sub>2</sub>, with the upper solubility limit not exceeding 10 mol.% at room temperature. There exists a two-phase region of trigonal and hexagonal borohydrides within the compositional range <i>x </i>= 0.8-0.9 at room temperature. Infrared spectra show splitting of various vibrational modes, indicating the presence of two cations in the trigonal Mg<i><sub>x</sub></i>Mn<sub>(1−</sub><i><sub>x</sub></i><sub>)</sub>(BH<sub>4</sub>)<sub>2</sub> solid solutions, as well as the appearance of a second phase, hexagonal α-Mg(BH<sub>4</sub>)<sub>2</sub>, at higher magnesium contents. All vibrational frequencies are shifted to higher values with increasing magnesium content. The decomposition temperature of the trigonal Mg<i><sub>x</sub></i>Mn<sub>(1−</sub><i><sub>x</sub></i><sub>)</sub>(BH<sub>4</sub>)<sub>2</sub> (<i>x = </i>0-0.8) does not vary significantly as a function of the magnesium content (433-453 K). The desorbed gas contains mostly hydrogen and 3-7.5 mol.% diborane B<sub>2</sub>H<sub>6</sub>, as determined from analyses of the Mn(BH<sub>4</sub>)<sub>2</sub> and Mg<sub>0.5</sub>Mn<sub>0.5</sub>(BH<sub>4</sub>)<sub>2</sub> samples. An eutectic relation between α-Mg(BH<sub>4</sub>)<sub>2</sub> and LiBH<sub>4</sub> is observed. The solid solution Mg<i><sub>x</sub></i>Mn<sub>(1−</sub><i><sub>x</sub></i><sub>)</sub>(BH<sub>4</sub>)<sub>2</sub> is a promising material for hydrogen storage as it decomposes at a similar temperature to Mn(BH<sub>4</sub>)<sub>2</sub>, i.e. at a much lower temperature than pure Mg(BH<sub>4</sub>)<sub>2</sub> without significantly losing hydrogen weight capacity thanks to substitution of Mn by Mg up to 80 mol.%. The questions of diborane release and reversibility remain to be addressed.
dc.language.isoen
dc.publisherElsevier
dc.subject.enHydrides
dc.subject.enHydrogen storage
dc.subject.enSynchrotron radiation
dc.typeArticle de revue
dc.identifier.doi10.1016/j.actamat.2011.04.052
dc.subject.halChimie/Matériaux
bordeaux.journalActa Materialia
bordeaux.page5171-5180
bordeaux.volume59
bordeaux.issue13
bordeaux.peerReviewedoui
hal.identifierhal-00606790
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00606790v1
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