Hydrogen Desorption in Mg(BH4)2-Ca(BH4)2 System

Magnesium borohydride, Mg(BH4)2, and calcium borohydride, Ca(BH4)2, are promising materials for hydrogen storage. Mixtures of different borohydrides have been the subject of numerous researches; however, the whole Mg(BH4)2-Ca(BH4)2 system has not been investigated yet. In this study, the phase stability and the hydrogen desorption were experimentally investigated in the Mg(BH4)2-Ca(BH4)2 system, by means of XRD, ATR-IR, and HP-DSC. Mg(BH4)2 and Ca(BH4)2 are fully immiscible in the solid state. In the mechanical mixtures, thermal decomposition occurs at slightly lower temperatures than for pure compounds. However, they originate products that cannot be identified by XRD, apart from Mg and MgH2. In fact, amorphous phases or mixtures of different poorly crystalline or nanocrystalline phases are formed, leading to a limited reversibility of the system.

[1]  Lars H. Jepsen,et al.  Phase Diagram for the NaBH4–KBH4 System and the Stability of a Na1–xKxBH4 Solid Solution , 2015 .

[2]  A. Züttel,et al.  In situ synchrotron diffraction studies of phase transitions and thermal decomposition of Mg(BH4)2 and Ca(BH4)2 , 2007 .

[3]  Elsa Roedern,et al.  Eutectic melting of LiBH4-KBH4. , 2014, Physical chemistry chemical physics : PCCP.

[4]  H. Hagemann,et al.  Insight into Mg(BH4)2 with synchrotron X-ray diffraction: Structure revision, crystal chemistry, and anomalous thermal expansion , 2009 .

[5]  Y. Filinchuk,et al.  Facile synthesis of anhydrous alkaline earth metal dodecaborates MB12H12 (M = Mg, Ca) from M(BH4)2. , 2015, Dalton transactions.

[6]  Lars H. Jepsen,et al.  Metal borohydrides and derivatives - synthesis, structure and properties. , 2017, Chemical Society reviews.

[7]  S. Orimo,et al.  Reversible dehydrogenation of magnesium borohydride to magnesium triborane in the solid state under moderate conditions. , 2011, Chemical communications.

[8]  G. Soloveichik,et al.  Magnesium borohydride as a hydrogen storage material: Properties and dehydrogenation pathway of unsolvated Mg(BH4)2 , 2009 .

[9]  M. Paskevicius,et al.  Eutectic melting in metal borohydrides. , 2013, Physical chemistry chemical physics : PCCP.

[10]  O. Zavorotynska,et al.  Kinetics studies of the reversible partial decomposition reaction in Mg(BH4)2 , 2016 .

[11]  A. Ibikunle,et al.  Kinetics and modeling study of a Mg(BH4)2/Ca(BH4)2 destabilized system , 2012 .

[12]  H. Hagemann,et al.  New fundamental experimental studies on α-Mg(BH4)2 and other borohydrides , 2011 .

[13]  I. Saldan,et al.  Structural Changes Observed during the Reversible Hydrogenation of Mg(BH4)2 with Ni-Based Additives , 2014 .

[14]  M. D. Baró,et al.  Ca(BH4)2 + MgH2: Desorption Reaction and Role of Mg on Its Reversibility , 2013 .

[15]  B. Civalleri,et al.  Thermodynamic modelling of Mg(BH4)2 , 2015 .

[16]  Young-Su Lee,et al.  Hydrogen Back-Pressure Effects on the Dehydrogenation Reactions of Ca(BH_4)_2 , 2012 .

[17]  M. Dornheim,et al.  Exploring Ternary and Quaternary Mixtures in the LiBH4 -NaBH4 -KBH4 -Mg(BH4 )2 -Ca(BH4 )2 System. , 2019, Chemphyschem : a European journal of chemical physics and physical chemistry.

[18]  F. Teixidor,et al.  Experimental Evidence of Ca[B12H12] Formation During Decomposition of a Ca(BH4)2 + MgH2 Based Reactive Hydride Composite , 2011 .

[19]  M. Dornheim,et al.  Reactive Hydride Composite of Mg2NiH4 with Borohydrides Eutectic Mixtures , 2018 .

[20]  E. Ronnebro Development of group II borohydrides as hydrogen storage materials , 2011 .

[21]  V. Stavila,et al.  Structure-dependent vibrational dynamics of Mg(BH4)2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations. , 2016, Physical chemistry chemical physics : PCCP.

[22]  Duane D. Johnson,et al.  On the Reversibility of Hydrogen-Storage Reactions in Ca(BH4)2: Characterization via Experiment and Theory , 2009 .

[23]  H. Hagemann,et al.  Vibrational spectra and structure of borohydrides , 2013 .

[24]  Zaiping Guo,et al.  Study on the dehydrogenation kinetics and thermodynamics of Ca(BH4)2 , 2010 .

[25]  D. Sholl,et al.  First-Principles Characterization of Amorphous Phases of MB12H12, M = Mg, Ca , 2010 .

[26]  H. Hagemann,et al.  The first crystallographic and spectroscopic characterization of a 3d-Metal borohydride: Mn(BH4)2 , 2009 .

[27]  M. Fichtner,et al.  On the rehydrogenation of decomposed Ca(BH4)2 , 2015 .

[28]  M. Corno,et al.  A thermodynamic investigation of the LiBH4–NaBH4 system , 2016 .

[29]  A. Ibikunle,et al.  Hydrogen storage in destabilized borohydride materials , 2010 .

[30]  A. Züttel,et al.  Complex hydrides for hydrogen storage. , 2007, Chemical reviews.

[31]  J. Shim,et al.  On the reversibility of hydrogen storage in Ti- and Nb-catalyzed Ca(BH4)2 , 2008 .

[32]  Christopher M Wolverton,et al.  First-principles prediction of thermodynamically reversible hydrogen storage reactions in the Li-Mg-Ca-B-H system. , 2009, Journal of the American Chemical Society.

[33]  A. Züttel,et al.  Supercritical N2 processing as a route to the clean dehydrogenation of porous Mg(BH4)2. , 2014, Journal of the American Chemical Society.

[34]  M. Corno,et al.  Phase diagrams of the LiBH4-NaBH4-KBH4 system. , 2017, Physical chemistry chemical physics : PCCP.

[35]  H. Wenk,et al.  MAUD: a friendly Java program for material analysis using diffraction , 1999 .

[36]  H. Hagemann,et al.  Vibrational Spectra of Ca(BH4)2 , 2008 .

[37]  J. R. Downing,et al.  Chemistry of Boranes. III.1 The Infrared and Raman Spectra of B12H12 - and Related Anions , 1962 .

[38]  M. Corno,et al.  Halide Substitution in Magnesium Borohydride , 2012 .

[39]  S. Orimo,et al.  Selective reversible hydrogenation of Mg(B3H8)2/MgH2 to Mg(BH4)2: pathway to reversible borane-based hydrogen storage? , 2015, Inorganic chemistry.

[40]  Y. Filinchuk,et al.  Complex hydrides for energy storage , 2019, International Journal of Hydrogen Energy.

[41]  P. Jena,et al.  Intermediate Phases during Decomposition of Metal Borohydrides, M(BH4)n (M = Na, Mg, Y) , 2014 .

[42]  E. M. Dematteis,et al.  Phase stability and hydrogen desorption in a quinary equimolar mixture of light-metals borohydrides , 2018, International Journal of Hydrogen Energy.

[43]  Young-Su Lee,et al.  Identification of the Dehydrogenated Product of Ca(BH4)2 , 2009 .

[44]  Yang Song,et al.  High-Pressure Structures and Transformations of Calcium Borohydride Probed by Combined Raman and Infrared Spectroscopies , 2010 .

[45]  H. Hagemann,et al.  FT-IR spectra of inorganic borohydrides. , 2014, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[46]  S. Bordiga,et al.  Spectroscopic and Structural Characterization of Thermal Decomposition of γ-Mg(BH4)2: Dynamic Vacuum versus H2 Atmosphere , 2015 .