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Nanostructured, complex hydride systems for hydrogen generation

Department of Mechanical and Mechatronics Engineering, University of Waterloo, 200 University Ave. W., Waterloo, Ontario, Canada N2L 3G1

Special Issues: Materials for Energy Technologies

Complex hydride systems for hydrogen (H2) generation for supplying fuel cells are being reviewed. In the first group, the hydride systems that are capable of generating H2 through a mechanical dehydrogenation phenomenon at the ambient temperature are discussed. There are few quite diverse systems in this group such as lithium alanate (LiAlH4) with the following additives: nanoiron (n-Fe), lithium amide (LiNH2) (a hydride/hydride system) and manganese chloride MnCl2 (a hydride/halide system). Another hydride/hydride system consists of lithium amide (LiNH2) and magnesium hydride (MgH2), and finally, there is a LiBH4-FeCl2 (hydride/halide) system. These hydride systems are capable of releasing from ~4 to 7 wt.% H2 at the ambient temperature during a reasonably short duration of ball milling. The second group encompasses systems that generate H2 at slightly elevated temperature (up to 100 °C). In this group lithium alanate (LiAlH4) ball milled with the nano-Fe and nano-TiN/TiC/ZrC additives is a prominent system that can relatively quickly generate up to 7 wt.% H2 at 100 °C. The other hydride is manganese borohydride (Mn(BH4)2) obtained by mechano-chemical activation synthesis (MCAS). In a ball milled (2LiBH4 + MnCl2) nanocomposite, Mn(BH4)2 co-existing with LiCl can desorb ~4.5 wt.% H2 at 100 °C within a reasonable duration of dehydrogenation. Practical application aspects of hydride systems for H2 generation/storage are also briefly discussed.
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Keywords hydrogen generation; mechano-chemical activation synthesis; mechanical dehydrogenation; thermal dehydrogenation

Citation: Robert A. Varin, Amirreza Shirani Bidabadi. Nanostructured, complex hydride systems for hydrogen generation. AIMS Energy, 2015, 3(1): 121-143. doi: 10.3934/energy.2015.1.121


  • 1. Scott DS (2007) Smelling land-the hydrogen defense against climate catastrophe, Westmount, QC: Canadian Hydrogen Association.
  • 2. Bockris JOM (2007) Will lack of energy lead to the demise of high-technology countries in this century? Int J Hydrogen Energ 32: 153-158.    
  • 3. Varin RA, T. Czujko T, Wronski ZS (2009) Nanomaterials for solid state hydrogen storage. New York, Springer Science, 2009. Business Media.
  • 4. Varin RA, Wronski ZS (2013) Progress in hydrogen storage in complex hydrides. In: Gandia LM, Arzamendi G, Diéguez PM, Renewable Hydrogen Technologies. Production, Purification, Storage, Applications and Safety, Elsevier: Ch. 13; 293-332.
  • 5. Yang J, Sudik A, Wolverton C, et al. (2010) High capacity hydrogen storage materials: attributes for automotive applications and techniques for materials discovery. Chem Soc Rev 39: 656-675.    
  • 6. Rude LH, Nielsen TK, Ravnsbæk DB, et al. (2011) Tailoring properties of borohydrides for hydrogen storage: A review. Phys Status Solidi A 208: 1754-1773.    
  • 7. Department of Energy US. Available from: http://energy.gov/sites/prod/files/2014/03/f12/targets_onboard_hydro_storage.pdf.
  • 8. Li H-W, Yan Y, Orimo S-I, et al. (2011) Recent progress in metal borohydrides for hydrogen storage. Energies 4: 185-214.    
  • 9. Toyota Hydrogen Fuel Cell Vehicles to be Available in 2016. Available from: http://www.hngn.com/articles/33584/20140612/toyota-hydrogen-fuel-cell-vehicles-to-be-available-in-2016.htm.
  • 10. Hyundai first to offer hydrogen fuel cell vehicles to Canadian public. Available from: http://www.newswire.ca/en/story/1453489/hyundai-first-to-offer-hydrogen-fuel-cell-vehicles-to-canadian-public.
  • 11. Calka A, Radlinski AP (1991) Universal high performance ball-milling device and its application for mechanical alloying. Mater Sci Eng A 134: 1350-1353.    
  • 12. Patents: WO9104810, US5383615, CA2066740, EP0494899, AU643949.
  • 13. Calka A, Varin RA (2001) Application of Controlled Ball Milling in Materials Processing. In: Srivatsan TS, Varin RA, Khor M, Int. Symp. on Processing and Fabrication of Advanced Materials IX (PFAM IX). ASM International: Materials Park, OH, 263-287.
  • 14. Varin RA, Parviz R (2012) The effects of the micrometric and nanometric iron (Fe) additives on the mechanical and thermal dehydrogenation of lithium alanate (LiAlH4), its self-discharge at low temperatures and rehydrogenation. Int J Hydrogen Energ 37: 9088-9102.    
  • 15. WebElements Periodic Table: the periodic table on the web. Available from: http://webelements.com.
  • 16. Varin RA, Parviz R (2014) The effects of the nanometric interstitial compounds TiC, ZrC and TiN on the mechanical and thermal dehydrogenation and rehydrogenation of the nanocomposite lithium alanate (LiAlH4) hydride. Int J Hydrogen Energ 39: 2575-2586.    
  • 17. Girgis K (1983) Structure of intermetallic compounds, In: Physical Metallurgy; third, revised and enlarged edition; Cahn RW and Haasen P, Elsevier Science Publishers, BV, Part I, Ch.5, 220-269.
  • 18. Varin RA, Zbroniec L (2012) Mechanical and thermal dehydrogenation of lithium alanate (LiAlH4) and lithium amide (LiNH2) hydride composites. Crystals 2: 159-175.    
  • 19. Varin RA, Zbroniec L (2010) The effects of nanometric nickel (Ni) catalyst on the dehydrogenation and rehydrogenation behavior of ball milled lithium alanate (LiAlH4). J Alloy Compd 506: 928-939.    
  • 20. Varin RA, Zbroniec L, Czujko T, Wronski ZS (2011) The effects of nanonickel additive on the decomposition of complex metal hydride LiAlH4 (lithium alanate). Int J Hydrogen Energ 36: 1167-1176.
  • 21. Varin RA, Parviz R, Zbroniec L, Wronski ZS (2012) Fundamental aspects of mechanical dehydrogenation of Li-based complex hydride nanocomposites and their self-discharge at low temperatures. Energy Procedia 29: 644-653.    
  • 22. Parviz R, Varin RA (2013) Combined effects of molar ratio and ball milling energy on the phase transformations and mechanical dehydrogenation in the lithium amide-magnesium hydride (LiNH2 + nMgH2) (n = 0.5-2.0) nanocomposites. Int J Hydrogen Energy 38: 8313-8327.    
  • 23. Varin RA, Parviz R, Polanski M, et al. (2014) The effect of milling energy input and molar ratio on the dehydrogenation and thermal conductivity of the (LiNH2 + nMgH2) (n = 0.5, 0.7, 0.9, 1.0, 1.5 and 2.0) nanocomposites. Int J Hydrogen Energ 39: 10585-10599.
  • 24. Orimo SI, Nakamori Y, Eliseo JR, et al. (2007) Complex hydrides for hydrogen storage. Chem Rev 107: 4111-4132.    
  • 25. Züttel A, Rentsch S, Fischer P, et al. (2003) Hydrogen storage properties LiBH4. J Alloys Compd 356-357: 515-520.
  • 26. Smith MB, Bass GE (Jr.) (1963) Heats and Free Energies of Formation of the Alkali Aluminum Hydrides and of Cesium Hydride. J Chem Eng Data 8: 342-346.    
  • 27. Mauron Ph, Buchter F, Friedrichs O, et al. (2008) Stability and reversibility of LiBH4. J Phys Chem 112: 906-910.    
  • 28. Nakamori Y, Miwa K, Ninomiya A, et al. (2006) Correlation between thermodynamical stabilities of metal borohydrides and cation electronegativities: First principle calculations and experiments. Phys Rev B 74: 045126 1-9.    
  • 29. Nakamori Y, Li HW, Kikuchi K, et al. (2007) Thermodynamical stabilities of metal-borohydrides. J Alloy Compd 446-447: 296-300.
  • 30. Varin RA, Shirani AB (2015) Rapid, ambient temperature hydrogen generation from the solid state Li-B-Fe-H system by mechano-chemical activation synthesis. J Power Sources (submitted, under revision).
  • 31. Schaeffer GW, Roscoe JS, Stewart AC (1956) The reduction of iron (III) chloride with lithium aluminohydride and lithium borohydride: iron (II) borohydride. J Amer Chem Soc 18: 729-733.
  • 32. Myakishev KG, Volkov VV (2006) Mechanochemical synthesis of diborane (6) by the interaction of anhydrous chloride of iron (II), cobalt (II), nickel (II) with tetrahydroborates of alkaline metals. Chem Suste Dev 14: 375-378.
  • 33. Liu XF, McGrady GS, Langmi HW, et al. (2009) Facile cycling of Ti-doped LiAlH4 for high performance hydrogen storage. J Am Chem Soc 131: 5032-5033.    
  • 34. Liu XF, Langmi HW, Beattie SD, et al. (2011) Ti doped LiAlH4 for hydrogen storage: synthesis, catalyst loading, and cyclic performance. J Am Chem Soc 133: 15593-15597.    
  • 35. Varin RA, Zbroniec L (2010) The effects of ball milling and nanometric nickel additive on the hydrogen desorption from lithium borohydride and manganese chloride (3LiBH4 + MnCl2) mixture. Int J Hydrogen Energ 35: 3588-3597.    
  • 36. Varin RA, Zbroniec L, Polanski M, et al. (2012) Mechano-chemical synthesis of manganese borohydride (Mn(BH4)2) and inverse cubic spinel (Li2MnCl4) in the (nLiBH4 + MnCl2) (n = 1, 2, 3, 5, 9 and 23) mixtures and their dehydrogenation behavior. Int J Hydrogen Energ 37: 16056-16069.    
  • 37. Varin RA, Bidabadi AS (2014) The effect of milling energy input during mechano-chemical activation synthesis (MCAS) of the nanocrystalline manganese borohydride (Mn(BH4)2) on its thermal dehydrogenation properties. Int J Hydrogen Energ 39: 11620-11632.    
  • 38. Černý R, Penin N, Hagemann H, et al. (2009) The first crystallographic and spectroscopic characterization of a 3d-metal borohydride: Mn(BH4)2. J Phys Chem C 113: 9003-9007.    
  • 39. Severa G, Hagemann H, Longhini M, et al. (2010) Thermal desorption, vibrational spectroscopic, and DFT computational studies of the complex manganese borohydrides Mn(BH4)2 and [Mn(BH4)4]2-. J Phys Chem C 114: 15516-15521.    
  • 40. Černý R, Penin N, D'Anna V, et al. (2011) MgxMn(1-x)(BH4)2 (x = 0-0.8), a cation solid solution in a bimetallic borohydride . Acta Materialia 59: 5171-5180.
  • 41. Sandrock G, Gross K, Thomas G, et al. (2002) Engineering considerations in the use of catalyzed sodium alanates for hydrogen storage. J Alloy Compd 332: 696-701.
  • 42. Sandrock G, Gross K, Thomas G (2002) Effect of Ti-catalyst content on the reversible hydrogen storage properties of the sodium alanates. J Alloy Compd 339: 299-308.    
  • 43. Yvon K, Lorenzoni JL (2006) Hydrogen-powered lawn mower: 14 years of operation. Int J Hydrogen Energ 31: 1763-1767.    


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Copyright Info: 2015, Robert A. Varin, et al., licensee AIMS Press. This is an open access article distributed under the terms of the Creative Commons Attribution Licese (http://creativecommons.org/licenses/by/4.0)

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