Dynamics

The dynamics of LiBH₄ was investigated by nuclear magnetic resonance [62] and by neu-tron scattering experiments. Quasi-elastic neuneu-tron scattering experiments was performed on LiBH₄ with the aim to investigate the hydrogen reorientational dynamics [53, 63]. In the LT-phase, [BH₄] tetrahedra undergo predominantly 120^◦ rotations around the C₃ symmetry axis. At high temperatures, instead, the large thermal ellipsoids detected from X-ray diffrac-tion measurements suggested a disordered rotadiffrac-tional mechanism, and Verdalet al. concluded that the hydrogen motions can be described by quasi-free rotations of atoms around the C₃ axis, superimposed on a tumbling motion of the axial hydrogen. The diffusion coefficient of the [BH₄] units was also measured at temperatures above the melting point [64]. Using quasi-elastic neutron scattering experiments, the apparent diffusion coefficient at 573 K is

Figure 1.8: Low temperature LiBH₄ orthorhombic crystal structure (P nma) [59]. Big orange spheres:

lithium, green spheres: boron, small grey spheres: hydrogen. Structure parameters: a= 7.141Å,b= 4.431Å andc= 6.748Å. The angle between H-B-H is in the range108.8^◦−109.9^◦.

Figure 1.9: High temperature LiBH4hexagonal crystal structure (P63mc) [57]. Big orange spheres: lithium, green spheres: boron, small grey spheres: hydrogen. Structure parameters: a= 4.27631Å andc= 6.94844Å.

The angle between H-B-H is in the range106^◦−112^◦.

Figure 1.10: Simplified phase diagram of LiBH4: a reversible phase transition takes place at108^◦C(381 K), from an orthorhombic to an hexagonal crystal structure. At∼268^◦C(∼541 K), LiBH4 melts (L), and the decomposition starts above∼380^◦C(∼650 K).

D_s= 5.3·10⁻⁵cm²/s, increasing to D_s= 7.9·10⁻⁵cm²/s at 753 K.

Recently, it was shown that LiBH₄ exhibits a high Li⁺- ion conductivity in the HT crys-tal modification and in solid solution with LiI [65]. The superionic transition is thought to be coupled with order/disorder transition which is characteristic for LiBH4 [66, 60].

Most experimental studies of hydrogen sorption properties require intensive ball milled materials. It is a usual procedure in order to increase the material active surface, and there-fore improving gas sorption properties. As shown in previous work [67], ball milling is shown to affect the structural phase transition, altering the endothermic peak in the LT → HT crystal phase transition and the lattice parameters in the LT crystal modification.

In this work, a quasi-elastic experiment has been performed on different ball milled sam-ples to elucidate the hydrogen dynamics across the crystal phase transition, and the possible influence of mechanical treatment on the microscopic hydrogen dynamics (see chapter 4).

1.4.6 Magnesium Borohydride (Mg(BH₄)₂)

Magnesium borohydride was first synthesized in the 1950s, but the interest in hydrogen en-ergy made it a possible candidate for hydrogen storage. It is characterised by a gravimetric and volumetric storage density of 14.9 wt% and 90 kg/m³ H2, [23, 68]. Moreover the ma-terial is interesting due to its overall reaction enthalpy ∆H, reported values (for desorption to MgH₂) are in the range −40 to −57 kJ/mol H₂ [69, 70] which is in the range suitable for storage applications. However, reaction kinetics is sluggish, and Mg(BH₄)₂ decomposes above∼300^◦C(573 K) in a multi step process [71,72] and its limited reversibility [73] makes it unsuitable for practical application, so far.

Magnesium borohydride exists in various crystalline forms, as recently discovered and char-acterized by X-ray and neutron scattering techniques [74, 75, 76]. Among the observed polymorphs of Mg(BH4)2, namely α, β, γ and δ-phase, the low-temperature (LT) α-phase and the high-temperature (HT) β-phase are the most commonly investigated for hydrogen storage applications [73].

1.4.6.1 Structure

The first low- temperature (LT) and high- temperature (HT) crystal phases were identified by Her et al. [77]. In that work, a LT α phase was identified with an hexagonal structure and space groupP61. Later, this phase was refined using a combination of X-ray diffraction on single crystal and neutron diffraction on powder, yielding a lower symmetry space group P6₁22[78]. The hexagonal crystal structure is characterized by a unit cell volume of 3434 ų

Figure 1.11: Crystal structure of α−-Mg(BH4)2 along thec axis: magnesium atoms are represented by orange spheres, boron by green and hydrogen by grey spheres.

and the lattice parameters show a non-linear thermal expansion over a wide range of tem-peratures. The structure is also characterized by six non-equivalent positions of the [BH₄] units, giving a strongly anisotropic environment for the tetrahedron. Theα-Mg(BH₄)₂is also characterized by unoccupied voids (37ų) along the (00z) direction which are not present in the β-polymorph.

The LT α-phase transforms into a HT β-phase at 490 K, and the β-phase is metastable when it is cooled to room temperature. It is characterized by an orthorhombic crystal structure with aF dddsymmetry. The unit volume cell is double of theα-phase,7543ų, and the crystal structure does not contain any voids. The structure is characterized by five non-equivalent positions of the [BH₄] units, yielding as well to a strongly anisotropic environment.

X-ray and neutron diffraction on both polymorphs showed a non linear thermal expansion of lattice parameters [78], but the effect is more pronounced in β-Mg(BH₄)₂. Indeed, lattice parameters show maxima and minima in the thermal range 100 - 500 K, leading to a strong anharmonicity of the system even at low temperature. This may be related to the change in the free energy profile and therefore a possible reason for the non-reversibility of the α→β transition.

In both phases, Mg atoms are surrounded by four [BH₄] tetrahedra leading to a strongly distorted tetrahedral environment, and at local level, the [BH₄] groups are facing the Mg atoms via two opposite edges of the tetrahedra, leading to an almost linear configuration Mg-B-Mg and a bidentate orientation of the Mg with respect to the bridging hydrogens [78, 77]

(see fig. 1.14). Fig. 1.13 shows a simplified phase diagram of Mg(BH₄)₂ at atmospheric pressure.

Despite the numerous studies, a full understanding of the ground state structures, hy-drogen bonding and gas release is still missing. Extensive theoretical calculations show that

Figure 1.12: Crystal structure of β−.Mg(BH4)2 along the c axis: magnesium atoms are represented by orange spheres, boron by green and hydrogen by grey spheres.

1 0 0 2 0 0 3 0 0 4 0 0

β- F d d d

α- P 6 ₁ 2 2

Temperature [°C]

β- F d d d

M g + 2 B + 4 H ₂

M e t a s t a b l e

4 0 0 5 0 0 6 0 0

Temperature [K]

Figure 1.13: Simplified phase diagram of Mg(BH4)2. The LTα-Mg(BH₄)2 transforms intoβ-Mg(BH₄)2

at ∼ 210^◦C (∼480 K). The β-polymorph is then metastable at room temperature, and the shaded area represents the metastable region. Above300^◦C(573 K), the decomposition process starts.

C 2||

C 2 C

3

Mg Mg

Figure 1.14: Idealized configuration of the [BH4] units in the Mg environment. The [BH4] unit lies almost in the line between two Mg atoms in a linear configuration. The three rotation axis are shown: the 3-fold 120^◦rotation axis C3, and the 2-fold 180^◦rotation axes (C_2|| and C2⊥). (large orange sphere) magnesium, (green spheres) boron, (small grey spheres) hydrogen.

the ground state is energetically almost degenerate and a variety of different structures that are very close in energy have been proposed, among the experimentally found α-phase [79].

A recent work [80], showed that, including van der Waals interactions, the lowest energy structure is the experimentally observed α-phase. Conversely, Caputoet al. [81], using com-putational methodology combining cluster optimization, simulated annealing based crystal structure prediction, periodic DFT total energy calculations and Symmetry Group Rela-tions analysis, found other crystal structures with lower energies. The rich polymorphism of Mg(BH₄)₂ could be partially attributed to the partial covalent bonding between Mg²⁺

and [BH₄]⁻ [75]. Still, the question about theoretical predicted and experimentally observed structures is open. The β-phase is energetically less favourable than the α-phase, as shown by DFT calculations [82, 83, 84], but the origin for the non-reversibility of the structural phase transition is not clear yet.