Robin Gremaud

An optical method to determine the thermodynamics of hydrogen absorption and desorption in metals

Hydrogenography, an optical high-throughput combinatorial technique to find hydrogen storage materials, has so far been applied only to materials undergoing a metal-to-semiconductor transition during hydrogenation. We show here that this technique works equally well for metallic hydrides. Additionally, we find that the thermodynamic data obtained optically on thin Pd–H films agree very well with Pd–H bulk data. This confirms that hydrogenography is a valuable general method to determine the relevant parameters for hydrogen storage in metal hydrides.

Low‐Temperature Synthesis of LiBH4 by Gas–Solid Reaction

The solvent-free synthesis of LiBH(4) from LiH in a borane atmosphere at 120 degrees C and ambient pressures is demonstrated. The source of borane is a milled LiBH(4)/ZnCl(2) mixture, in which Zn(BH(4))(2) is generated by a metathesis reaction. The yield of the reaction of about 74 % LiBH(4) shows that a bulk reaction is taking place upon borane absorption by LiH. This indicates that the formation of B-H bonds is the limiting step for the formation of LiBH(4) from the elements. Therefore, the use of diborane as a starting reactant allows one to circumvent the reaction barrier for the B-B bond dissociation and explains the rather moderate synthesis conditions.

Vibrational Dynamics of LiBH4 by Infrared Pump-Probe and 2D Spectroscopy

Employing femtosecond IR pump-probe and 2D spectroscopy, we measure the vibrational dynamics of LiBH(4) and several of its deuterium isotopomers. We find that the vibrational lifetime of various BH and BD stretching modes uniformly is approximately 1.5 ps for all BH(4-x)D(x)(-) units (0 <or=x <or=4). Subsequently, vibrational energy cascades down through BH and BD bending, facilitated by a strong Fermi resonance, into external (librational and translational) modes with a 3 ps time constant. Final thermalization of the energy is completed in about 100 ps. The vibrational spectra are purely homogeneously broadened indicating low inhomogeneity due to static disorder. We furthermore measured the anharmonic constants of various modes, which sets the benchmark for future ab initio calculations, and completed the first FTIR assignment of the stretching vibrations for the five BH(4-x)D(x)(-) units.

Hydrogen tracer diffusion in LiBH4 measured by spatially resolved Raman spectroscopy

The hydrogen tracer diffusion in LiBH(4) has been determined by spatially resolved Raman spectroscopy. The measurements give direct evidence of a macroscopic diffusion of BH ions as well as atomic exchange of hydrogen between the anions. An effective tracer diffusion coefficient of deuterium in LiBH(4) of D approximately 7 x 10(-14) m(2) s(-1) at 473 K is derived. The direct exchange rate of hydrogen between BH(4) units is 10 orders of magnitude slower, i.e. the relatively fast effective hydrogen diffusion has its origin in the fast diffusion of BH(4) units.

Anharmonicity in LiBH4–LiI induced by anion exchange and temperature

The feasibility of spatially resolved Raman spectroscopy probing diffusion multiples as a high-throughput method to study phase transformations in Li-ion conductors is demonstrated. The method is applied to the pseudobinary LiBH4–LiI system, which shows high Li-ion conductivity in the HT-phase of LiBH4. The vibrational properties measured as a function of composition and temperature corroborate the formation of a solid solution of Li(BH4)1−cIc over nearly the entire phase diagram (0<c≤0.8±0.2). The results shed light on anharmonic effects responsible for the structural phase transformation in this system.

Mobility and dynamics in the complex hydrides LiAlH4 and LiBH4

The dynamics and bonding of the complex hydrides LiBH4 and LiAlH4 have been investigated by vibrational spectroscopy. The combination of infrared, Raman, and inelastic neutron scattering (INS) spectroscopies on hydrided and deuterided samples reveals a complete picture of the dynamics of the BH4- and AlH4 anions respectively as well as the lattice. The straightforward interpretation of isotope effects facilitates tracer diffusion experiments revealing the diffusion coefficients of hydrogen containing species in LiBH4, and LiAlH4. LiBH4 exchanges atomic hydrogen starting at 200 degrees C. Despite having an iso-electronic structure, the mobility of hydrogen in LiAlH4 is different from that of LiBH4. Upon ball-milling of LiAlH4 and LiAlD4, hydrogen is exchanged with deuterium even at room temperature. However, the exchange reaction competes with the decomposition of the compound. The diffusion coefficients of the alanate and borohydride have been found to be D approximately equal 7 x 10(-14) m2 s(-1) at 473 K and D approximately equal 5 x 10(-16) m2 s(-1) at 348 K, respectively. The BH4 ion is easily exchanged by other ions such as I- or by NH2-. This opens the possibility of tailoring physical properties such as the temperature of the phase transition linked to the Li-ion conductivity in LiBH4 as measured by nuclear magnetic resonance and Raman spectroscopy. Temperature dependent Raman measurements on diffusion gradient samples Li(BH4)1-cIc demonstrate that increasing temperature has a similar impact to increasing the iodide concentration c: the system is driven towards the high-temperature phase of LiBH4. The influence of anion exchange on the hydrogen sorption properties is limited, though. For example, Li4(BH4)(NH2)3 does not exchange hydrogen easily even in the melt.

Hydrogen Dynamics in Lightweight Tetrahydroborates

Abstract The high hydrogen content in complex hydrides such as M[AlH4]x and M[BH4]x (M = Li, Na, K, Mg, Ca) stimulated many research activities to utilize them as hydrogen storage materials. An understanding of the dynamical properties on the molecular level is important to understand and to improve the sorption kinetics. Hydrogen dynamics in complex hydrides comprise long range translational diffusion as well as localized motions like vibrations, librations or rotations. All the different motions are characterized by their specific length- and timescales. Within this review we give an introduction to the physical properties of lightweight complex hydrides and illustrate the huge variety of dynamical phenomena on selected examples.

Hydrogen diffusion in NaH as derived from isotope exchange experiments

We report on hydrogen-deuterium-exchange experiments on NaH probed by thermogravimetry. From the measurements a diffusion parameter of deuterium in NaH of D=1.1×10−17 m2/s at 523 K is derived. The activation energy of tracer diffusion of D in NaH is found to be 1.0 eV. The results are hints for a diffusion process mediated by neutral hydrogen vacancies.

Lightweight sodium alanate thin films grown by reactive sputtering

We report the preparation of sodium alanate, a promising hydrogen storage material, in a thin film form using cosputtering in a reactive atmosphere of atomic hydrogen. We study the phase formation and distribution, and the hydrogen desorption, with a combination of optical and infrared transmission spectroscopy. We show that the hydrogen desorption, the phase segregation, and the role of the dopants in these complex metal hydrides can be monitored with optical measurements. This result shows that a thin film approach can be used for a model study of technologically relevant lightweight metal hydrides.

Evidence for Hydrogen Transport in Deuterated LiBH 4 from Raman-scattering Measurements and First-principles Calculations

Note: Times Cited: 0 Reference EPFL-ARTICLE-205909doi:10.4028/www.scientific.net/AST.72.150 URL: ://INSPEC:14355555 Record created on 2015-03-03, modified on 2016-08-09