Elastic versus Alloying Effects in Mg-Based Hydride Films.

Magnesium thin films covered with a layer of Pd absorb hydrogen at much higher pressures than bulk Mg. Such an effect was originally explained as a consequence of elastic clamping on Mg by the capping Pd layer. An alternative interpretation later suggested that the pressure increase could originate from simple alloying between Mg and Pd. Here we resolve this controversy by measuring the hydrogenation and dehydrogenation isotherms of Mg-Pd thin film alloys over a wide range of compositions. Our results disentangle the effects of elastic clamping and alloying and highlight the role of plastic deformations.

Metal-hydrogen systems with an exceptionally large and tunable thermodynamic destabilization.

Hydrogen is a key element in the energy transition. Hydrogen-metal systems have been studied for various energy-related applications, e.g., for their use in reversible hydrogen storage, catalysis, hydrogen sensing, and rechargeable batteries. These applications depend strongly on the thermodynamics of the metal-hydrogen system. Therefore, tailoring the thermodynamics of metal-hydrogen interactions is crucial for tuning the properties of metal hydrides. Here we present a case of large metal hydride destabilization by elastic strain. The addition of small amounts of zirconium to yttrium leads to a compression of the yttrium lattice, which is maintained during (de)hydrogenation cycles. As a result, the equilibrium hydrogen pressure of YH2 ↔ YH3 can be rationally and precisely tuned up to five orders of magnitude at room temperature. This allows us to realize a hydrogen sensor which indicates the ambient hydrogen pressure over four orders of magnitude by an eye-visible color change.

Concentration dependence of hydrogen diffusion in clamped vanadium (0 0 1) films.

The chemical diffusion coefficient of hydrogen in a 50 nm thin film of vanadium (0 0 1) is measured as a function of concentration and temperature, well above the known phase boundaries. Arrhenius analysis of the tracer diffusion constants reveal large changes in the activation energy with concentration: from 0.10 at 0.05 in H V-1 to 0.5 eV at 0.2 in H V-1. The results are consistent with a change from tetrahedral to octahedral site occupancy, in that concentration range. The change in site occupancy is argued to be caused by the uniaxial expansion of the film originating from the combined hydrogen induced expansion and the clamping of the film to the substrate.

Nucleation and growth mechanisms of nano magnesium hydride from the hydrogen sorption kinetics.

We use a combination of hydrogenography and Johnson-Mehl-Avrami-Kolmogorov (JMAK) analyses to identify (1) the driving force dependence of the nucleation and growth mechanism of MgH2 in thin film multilayers of Mg (10 nm) and (2) the nucleation and growth mechanism of Mg in the earlier formed MgH2, i.e. the hydrogen desorption process. We conclude that JMAK may be successfully applied to obtain the nucleation and growth mechanism of hydrogen absorption. The desorption mechanism, however, is not simply the reverse of the absorption mechanism. We find evidence that the barrier for nucleation of Mg is small. The dehydrogenation probably involves the formation of voids, which is energetically more favorable than elastic and plastic deformation of the multilayer.

Hysteresis and the role of nucleation and growth in the hydrogenation of Mg nanolayers.

We investigated the hydrogenation of 3 and 10 nm Mg layers sandwiched between Ti using an optical transmission technique (hydrogenography). We observe in situ the two dimensional nucleation and growth of single hydride domains of up to several millimeters in diameter. The low density of nuclei points to preferential nucleation at heterogeneous sites. From an analysis of the growth kinetics we deduce an extremely large edge boundary energy, which we relate to the plastic deformations inherent to the 30% volume expansion of the MgH(2). We find that the nucleation and growth process affects the hysteresis between absorption and desorption. Especially, the absorption branch can be lowered when nucleation barriers are removed. Our results show that when discussing the effect of nano-structuring on hydrogenation it may be quite complex to distinguish the thermodynamic and kinetic effects involved.