Enhanced tunability of thermodynamic stability of complex hydrides by the incorporation of H- anions

First-principles calculations were employed to investigate hypothetical complex hydrides (M,M')4FeH8 (M = Na, Li; M'=Mg, Zn, Y, Al). Besides complex anion [FeH6]4-, these materials contain two H- anions, which raise the total anionic charge state from tetravalent to hexavalent, and thereby significantly increasing the number of combinations of countercations. We have determined that similar to complex hydrides (M,M')2FeH6 containing only [FeH6]4-, the thermodynamic stability is tuned by the average cation electronegativity. Thus, the chemical flexibility provided by incorporating H- enhances the tunability of thermodynamic stability, which will be beneficial in obtaining optimal stability for hydrogen storage materials

First-principles study on the intermediate compounds of LiBH4_4

We report the results of the first-principles calculation on the intermediate compounds of LiBH$_4$. The stability of LiB$_3$H$_8$ and Li$_2$B$_n$H$_n (n=5-12)$ has been examined with the ultrasoft pseudopotential method based on the density functional theory. Theoretical prediction has suggested that monoclinic Li$_2$B$_{12}$H$_{12}$ is the most stable among the candidate materials. We propose the following hydriding/dehydriding process of LiBH$_4$ via this intermediate compound : LiBH$_4 \leftrightarrow {1/12}$Li$_{2}$B$_{12}$H$_{12} + {5/6}$ LiH $+ {13/12}$H$_2 \leftrightarrow$LiH $+$ B $+ {3/2}$H$_2$. The hydrogen content and enthalpy of the first reaction are estimated to be 10 mass% and 56 kJ/mol H$_2$, respectively, and those of the second reaction are 4 mass% and 125 kJ/mol H$_2$. They are in good agreement with experimental results of the thermal desorption spectra of LiBH$_4$. Our calculation has predicted that the bending modes for the $\Gamma$-phonon frequencies of monoclinic Li$_2$B$_{12}$H$_{12}$ are lower than that of LiBH$_4$, while stretching modes are higher. These results are very useful for the experimental search and identification of possible intermediate compounds.Comment: 7 pages, 5 figures, submitted to PR

Lithium colloids and color center creation in electron-irradiated Li2NH observed by electron-spin resonance

4 pagesInternational audienceWe have irradiated Li2NH powder with MeV electrons at room temperature and investigated the introduced defects with electron spin resonance. CESR indicates the presence of nanosize metallic Li colloids seen as a Lorentzian line with a g = 2.0023 and a line width DeltaH = 50 microT. A second, broader, signal (DeltaH = 3 to 4 mT) appears superimposed upon the Li line at low T (Curie-type behavior) which exhibits complex T-dependence with a break near 180 K for its g-value and DeltaH. We are suggesting for the latter a vacancy-type defect in the NH-sublattice, with freezing of its H-component below 180 K. When heated both the Li colloids and the color centers anneal around 100 C probably due to hydrogen evolution and subsequent chemical degradation

Magnetization measurements on Li2Pd3B superconductor

Magnetization in DC magnetic fields and at different temperatures have been measured on the Li2Pd3B compound. This material was recently found to show superconductivity at 7-8K. Critical fields Hc1(0) and Hc2(0) have been determined to be 135Oe and 4T, respectively. Critical current density, scaling of the pinning force within the Kramer model and the irreversibility field data are presented. Several superconductivity parameters were deduced: x(csi)=9.1 nm, l(lamda)=194nm and k=21. The material resembles other boride superconductors from the investigated points of view.Comment: 10 pages, 5 figure

Complex transition metal hydrides incorporating ionic hydrogen: Synthesis and characterization of Na2Mg2FeH8 and Na2Mg2RuH8

A new class of quaternary complex transition metal hydrides (Na2Mg2TH8 (T = Fe, Ru)) have been synthesized and their structures determined by combined synchrotron radiation X-ray and powder neutron diffraction. The compounds can be considered as a link between ionic and complex hydrides in terms of incorporating independently coordinated ionic and covalent hydrogen. These novel isostructural complex transition metal hydrides crystallize in the orthorhombic space group Pbam, where the octahedral complex hydride anion is surrounded by a cubic array of four Mg2+ and four Na+ cations, forming distinct two-dimensional layers. An intriguing feature of these materials is the distorted octahedral coordination of the isolated H− anions by four Na+ and two Mg2+ cations, which form layers between the transition metal containing layers. The vibrational modes of the H− anions and complex hydride anion are independently observed for the first time in a quaternary complex transition metal hydride system by Raman and IR spectroscopy