TY - JOUR
T1 - Role of aluminum chloride on the reversible hydrogen storage properties of the Li-N-H system
AU - Fernández Albanesi, Luisa
AU - Garroni, Sebastiano
AU - Arneodo Larochette, Pierre
AU - Nolis, Pau
AU - Mulas, Gabriele
AU - Enzo, Stefano
AU - Baró, María Dolors
AU - Gennari, Fabiana C.
PY - 2015/1/1
Y1 - 2015/1/1
N2 - © 2015 Hydrogen Energy Publications, LLC. In order to understand the role of AlCl3 addition on the Li-N-H system, we have systematically investigated the hydrogen sorption kinetics and the reactions between LiNH2-LiH and AlCl3 additive with a multitechnique approach involving differential scanning calorimetry (DSC), hydrogen volumetric measurements, X-ray powder diffraction (XRPD), Fourier transform infrared analysis (FTIR) and solid-state nuclear magnetic resonance (NMR). Different interactions were identified as a function of the amount of added AlCl3. For low AlCl3 addition (0.03 mol), the Al3+ is incorporated into the interstitial sites by the LiNH2 structure. When AlCl3 amount increased (0.08 and 0.13 mol), the formation of new amide-chloride phases were detected by XRPD and indexed with cubic and hexagonal Li-Al-N-H-Cl geometries. Occurrence of such new phases was also confirmed by FTIR and NMR. The formation of these new Li-Al-N-H-Cl phases modifies the kinetics as well as the thermodynamic behavior of the original Li-N-H system. Interesting, in all AlCl3-doped composites, hydrogen was stored reversibly with faster sorption kinetics than un-doped Li-N-H system and with a significant reduction of NH3 emission. This improvement can be associated with the Al3+ incorporation into LiNH2 that promotes the migration of Li+, while for high AlCl3 doping, the formation of new phases Li-Al-N-H-Cl also weakens the N-H bond.
AB - © 2015 Hydrogen Energy Publications, LLC. In order to understand the role of AlCl3 addition on the Li-N-H system, we have systematically investigated the hydrogen sorption kinetics and the reactions between LiNH2-LiH and AlCl3 additive with a multitechnique approach involving differential scanning calorimetry (DSC), hydrogen volumetric measurements, X-ray powder diffraction (XRPD), Fourier transform infrared analysis (FTIR) and solid-state nuclear magnetic resonance (NMR). Different interactions were identified as a function of the amount of added AlCl3. For low AlCl3 addition (0.03 mol), the Al3+ is incorporated into the interstitial sites by the LiNH2 structure. When AlCl3 amount increased (0.08 and 0.13 mol), the formation of new amide-chloride phases were detected by XRPD and indexed with cubic and hexagonal Li-Al-N-H-Cl geometries. Occurrence of such new phases was also confirmed by FTIR and NMR. The formation of these new Li-Al-N-H-Cl phases modifies the kinetics as well as the thermodynamic behavior of the original Li-N-H system. Interesting, in all AlCl3-doped composites, hydrogen was stored reversibly with faster sorption kinetics than un-doped Li-N-H system and with a significant reduction of NH3 emission. This improvement can be associated with the Al3+ incorporation into LiNH2 that promotes the migration of Li+, while for high AlCl3 doping, the formation of new phases Li-Al-N-H-Cl also weakens the N-H bond.
KW - Aluminum chloride
KW - Hydrogen storage material
KW - Kinetics and thermodynamics properties
KW - Lithium amide/Lithium hydride system
KW - XRPD
KW - ss-MAS-NMR
U2 - https://doi.org/10.1016/j.ijhydene.2015.08.030
DO - https://doi.org/10.1016/j.ijhydene.2015.08.030
M3 - Article
VL - 40
SP - 13506
EP - 13517
JO - International Journal of Hydrogen Energy
JF - International Journal of Hydrogen Energy
SN - 0360-3199
ER -