Investigations on the Mechanochemical Synthesis and Evaluation of Hydrides in the Dept. of Physical Chemistry of Materials – Argentina

Mechanochemical synthesis and evaluation of binary and complex hydrides have been performed since 2000 in the Department of Physical Chemistry of Materials, San Carlos de Bariloche, Río Negro, Argentina. First, systems such as Mg-Fe-H, Mg-Co-H and Mg-H hydride systems were thoroughly investigated. Their complex and binary hydrides were synthesized by mechanochemical processing [1-8]. The kinetic behaviour of magnesium hydride was notably enhanced by the addition of tiny amounts of LiBH4 and transition metal additives [9-11]. Then, borohydrides composed of rare earth and borohydrides composites were also obtained by ball milling and improved destabilized borohydrides systems were developed [12-15]. Finally, Li-NMg-
H amide systems were studied for hydrogen storage and CO separation from CO (1%)/H2 rich mixtures for purification purposes [16,17]. The main outcomes obtained in these lines are in this work summarized.

References
[1] F.C. Gennari, F.J. Castro, G. Urretavizcaya, Hydrogen desorption behavior from magnesium hydrides synthesized by reactive mechanical alloying, J. Alloys and Compd. 321 (2001) 46.
[2] F.C. Gennari, F.J. Castro, J.J. Andrade Gamboa, Synthesis of Mg2FeH6 by reactive mechanical alloying: formation and decomposition properties, J. Alloys and Compd. 339 (2002) 261.
[3] F. C. Gennari, F. J. Castro, Formation, composition and stability of Mg–Co compounds, J. Alloys and Compd. 396 (2005) 182.
[4] J.A. Puszkiel, P. Arneodo Larochette, F.C. Gennari, Thermodynamic and kinetic studies of Mg–Fe–H after mechanical milling followed by sintering, J. Alloys and Compd. 463 (2008) 134.
[5] J.A. Puszkiel, P. Arneodo Larochette, F.C. Gennari, Hydrogen storage properties of MgxFe (x: 2, 3 and 15) compounds produced by reactive ball milling, J. Power Sources 186 (2009) 185.
[6] M.G. Verón, H. Troiani, F.C. Gennari, Synergetic effect of Co and carbon nanotubes on MgH2 sorption properties, Carbon 49 (2011) 2413.
[7] J. Puszkiel, PhD. Thesis: Preparation, study and optimization of complex hydrides for hydrogen storage, Supervisor: F.C. Gennari, Co-Supervisor: P. Arneodo Larochette. PhD in Engineering Science, Universidad Nacional de Cuyo, Instituto Balseiro, 2012.
[8] J. A. Puszkiel, J. Andrade-Gamboa, F. C. Gennari, Recent progresses on the Mg-Co-H and Mg-Fe-H systems for hydrogen-energy storage applications, ACCEPTED for publication in the edited book "Emerging Materials for Energy Conversion and Storage” (Elsevier), 2017, ISBN: 978-0-12-813794-9.
[9] J.A. Puszkiel and F.C. Gennari, Reversible hydrogen storage in metal-doped Mg–LiBH4 composites, Scr. Mater. 60 (2009) 667.
[10] F.Cova, PhD Thesis: Development and modeling of 50MgH2-Ni hydride and its application in high capacity destabilized systems for hydrogen storage. Supervisor: P. Arneodo Larochette, Co-Supervisor: F.C. Gennari. PhD in Engineering Science, Universidad Nacional de Cuyo, Instituto Balseiro, 2016.
[11] F.C. Gennari and J.A. Puszkiel, Enhanced hydrogen sorption kinetics of Mg50Ni–LiBH4 composite by CeCl3 addition, J. Power Sources 195 (2010) 3266.
[12] Fabiana C. Gennari, Destabilization of LiBH4 by MH2 (M = Ce, La) for hydrogen storage: Nanostructural effects on the hydrogen sorption kinetics, Int. J. Hydrogen Energy 36 (2011) 15231.
[13] F.C. Gennari, L. Fernández Albanesi, J.A. Puszkiel, P. Arneodo Larochette, Reversible hydrogen storage from 6LiBH4-MCl3 (M = Ce, Gd) composites by in-situ formation of MH2, Int. J. Hydrogen energy 36 (2011) 563.
[14] F.C. Gennari, Improved hydrogen storage reversibility of LiBH4 destabilized by Y(BH4)3 and YH3, Int. J. Hydrogen energy 37 (2012) 18895.
[15] F. Cova, F. C. Gennari and P. Arneodo Larochette, CNT addition to the LiBH4–MgH2 composite: the effect of milling sequence on the hydrogen cycling properties, RSC Adv. 5 (2015) 90014.
[16] G. Amica, F. Cova, P. Arneodo Larochette and F. C. Gennari, Effective participation of Li4(NH2)3BH4 in the dehydrogenation pathway of the Mg(NH2)2–2LiH composite, Phys.Chem.Chem.Phys. 18 (2016) 17997.
[17] N.S. Gamba, G. Amica, P. Arneodo Larochette, F.C. Gennari, Interaction between Li2Mg(NH)2 and CO: Effect on the hydrogen storage behavior of the
Li4(NH2)3BH4 doped Mg(NH2)2-2LiH composite, Int. J. Hydrogen Energy 42 (2017) 6024.