Peter Ngene

Reversibility of the hydrogen desorption from NaBH4 by confinement in nanoporous carbon

NaBH4 is an interesting hydrogen storage material for mobile applications due to its high hydrogen content of 10.8 wt%. However, its practical use is hampered by the high temperatures (above 500 °C) required to release the hydrogen and by the non reversibility of the hydrogen sorption. In this study, we show that upon heating to 600 °C, bulk NaBH4 decomposed into Na and Na2B12H12, releasing the expected 8.1wt% of hydrogen. Nanosizing and confinement of NaBH4 in porous carbon resulted in much faster hydrogen desorption kinetics. The onset of hydrogen release was reduced from 470 °C for the bulk to below 250 °C for the nanocomposites. Furthermore, the dehydrogenated nanocomposites were partially rehydrogenated to form NaBH4, with the absorption of about 43% of the initial hydrogen capacity at relatively mild conditions (60 bar H2 and 325 °C). Reversibility in this system was limited due to partial loss of Na during dehydrogenation. The dehydrogenated boron compounds were almost fully rehydrogenated to NaBH4 (98%) when extra Na was added to the nanocomposites. To the best of our knowledge, this is the first time that reversibility for NaBH4 has been demonstrated.

The role of Ni in increasing the reversibility of the hydrogen release from nanoconfined LiBH4

Nanoconfinement and the use of catalysts are promising strategies to enhance the reversibility of hydrogen storage in light metal hydrides. We combined nanoconfinement of LiBH4 in nanoporous carbon with the addition of Ni. Samples were prepared by deposition of 5-6 nm Ni nanoparticles inside the porous carbon, followed by melt infiltration with LiBH4. The Ni addition has only a slight influence on the LiBH4 hydrogen desorption, but significantly enhances the subsequent uptake of hydrogen under mild conditions. Reversible, but limited, intercalation of Li is observed during hydrogen cycling. X-ray diffraction shows that the initial crystalline 5-6 nm Ni nanoparticles are not present anymore after melt infiltration with LiBH4. However, transmission electron microscopy showed Ni-containing nanoparticles in the samples. Extended X-ray absorption fine structure spectroscopy proved the presence of Ni(x)B phases with the Ni-B coordination numbers changing reversibly with dehydrogenation and rehydrogenation of the sample. Ni(x)B can act as a hydrogenation catalyst, but solid-state 11B NMR proved that the addition of Ni also enhanced the reversibility of the system by influencing the microstructure of the nanoconfined LiBH4 upon cycling.

Enhanced reversibility of H2 sorption in nanoconfined complex metal hydrides by alkali metal addition

Complex metal hydrides, containing up to 18 wt% H2, are attractive candidates for on-board hydrogen storage. However, only limited reversibility of H2 desorption is achieved under mild conditions, especially in the absence of catalysts. Nanoconfining the materials in porous matrixes facilitates rehydrogenation, but still full reversibility has been rarely achieved. We reveal the factors that limit the reversibility using NaAlH4 in a porous carbon matrix as a model system. Relatively large Al crystallites (>100 nm) are formed after desorption, migrating out of the mesopores of the matrix. However, their formation does not fundamentally limit the reversibility, as these crystallites react with Na(H) and H2 reforming nanoconfined NaAlH4 under relatively mild conditions. We show for the first time that the main limiting factor for the decayed cycling capacity is the loss of active alkali metal species. Evaporation losses are minor, even when dehydrogenating at 325 °C in vacuum. Significant losses (30–40%) occur upon the first hydrogen desorption run, and are attributed to the reaction of Na species with impurities in the carbon matrix. A one-time addition of extra Na compensates for this loss, leading to close to full reversibility (>90%) at 150 °C under 55 bar H2 pressure. A similar effect is found when adding extra Li species to nanoconfined LiBH4. For nanoconfined complex metal hydrides irreversible loss of the reactive alkali metal species due to reaction with impurities can act as a major loss mechanism. However, the one-time addition of extra alkali metal species is very effective in resolving this issue, leading to close to full cycling reversibility under relatively mild conditions even in the absence of catalysts.

Polymer‐Induced Surface Modifications of Pd‐based Thin Films Leading to Improved Kinetics in Hydrogen Sensing and Energy Storage Applications

The catalytic properties of Pd alloy thin films are enhanced by a thin sputtered PTFE coating, resulting in profound improvements in hydrogen adsorption and desorption in Pd-based and Pd-catalyzed hydrogen sensors and hydrogen storage materials. The remarkably enhanced catalytic performance is attributed to chemical modifications of the catalyst surface by the sputtered PTFE leading to a possible change in the binding strength of the intermediate species involved in the hydrogen sorption process.

Confinement Effects for Lithium Borohydride: Comparing Silica and Carbon Scaffolds

LiBH4 is a promising material for hydrogen storage and as a solid-state electrolyte for Li ion batteries. Confining LiBH4 in porous scaffolds improves its hydrogen desorption kinetics, reversibility, and Li+ conductivity, but little is known about the influence of the chemical nature of the scaffold. Here, quasielastic neutron scattering and calorimetric measurements were used to study support effects for LiBH4 confined in nanoporous silica and carbon scaffolds. Pore radii were varied from 8 Å to 20 nm, with increasing confinement effects observed with decreasing pore size. For similar pore sizes, the confinement effects were more pronounced for silica than for carbon scaffolds. The shift in the solid–solid phase transition temperature is much larger in silica than in carbon scaffolds with similar pore sizes. A LiBH4 layer near the pore walls shows profoundly different phase behavior than crystalline LiBH4. This layer thickness was 1.94 ± 0.13 nm for the silica and 1.41 ± 0.16 nm for the carbon scaffolds. Quasi-elastic neutron scattering confirmed that the fraction of LiBH4 with high hydrogen mobility is larger for the silica than for the carbon nanoscaffold. These results clearly show that in addition to the pore size the chemical nature of the scaffold also plays a significant role in determining the hydrogen mobility and interfacial layer thickness in nanoconfined metal hydrides.

Promotion of Hydrogen Desorption from Palladium Surfaces by Fluoropolymer Coating

The catalytic activity of Pd surfaces towards hydrogen desorption was significantly improved by a nanometer‐thin polytetrafluoroethylene (PTFE) layer, as shown by an enhancement in the permeability of a Pd membrane coated on the permeate side. The origin of this effect was found to be due to a lowering of the barrier for hydrogen desorption, as evidenced by a change in the rate‐limiting mechanism of hydrogen permeation through the membrane from desorption (un‐coated) to diffusion controlled. In situ X‐ray photoelectron spectroscopy (XPS) revealed the electronic structure of the sputtered PTFE. Apart from C–Fn subunits (n=1, 2, 3), we found that nonsaturated carbon atoms became hydrogenated during hydrogen permeation, which was indicative of an interaction between Pd and PTFE. This interaction was weak; no Pd−F bonds were formed. We thus attributed the effect to an increase in the hydrophobicity of the surface by the porous PTFE layer and to a promoter effect of hydrogen desorption as a result of electrostatic interactions between chemisorbed hydrogen and physisorbed PTFE.

Eye readable metal hydride based hydrogen tape sensor for health applications

Using the change in the intrinsic optical properties of YMg-based thin films upon exposure to hydrogen, we observe the presence of hydrogen at concentrations as low as 20 ppm just by a change in color. The eye-visible color change circumvents the use of any electronics in this device, thereby making it an inexpensive H2 detector. The detector shows high selectivity towards H2 in H2-O2 - mixtures, and responds within 20 s to 0.25% H2 in the presence of 18% O2.