High-capacity hydrogen storage in lithium and sodium amidoboranes


The safe and efficient storage of hydrogen is widely recognized as one of the key technological challenges in the transition towards a hydrogen-based energy economy1,2. Whereas hydrogen for transportation applications is currently stored using cryogenics or high pressure, there is substantial research and development activity in the use of novel condensed-phase hydride materials. However, the multiple-target criteria accepted as necessary for the successful implementation of such stores have not yet been met by any single material. Ammonia borane, NH3BH3, is one of a number of condensed-phase compounds that have received significant attention because of its reported release of 12 wt% hydrogen at moderate temperatures (150 C). However, the hydrogen purity suffers from the release of trace quantities of borazine. Here, we report that the related alkali-metal amidoboranes, LiNH2BH3 and NaNH2BH3, release 10.9 wt% and 7.5 wt% hydrogen, respectively, at significantly lower temperatures (90 C) with no borazine emission. The low-temperature release of a large amount of hydrogen is significant and provides the potential to fulfil many of the principal criteria required for an on-board hydrogen store.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Schematic diagram of the crystal structure of LiNH2BH3 and NaNH2BH3 determined from high-resolution X-ray powder diffraction data at room temperature.
Figure 2: High-field 289.2 MHz (21.2 T) 11B NMR of LiNH2BH3 and NH3BH3 samples.
Figure 3: TPD and DSC spectra.
Figure 4


  1. 1

    Schlapbach, L. & Zuttel, A. Hydrogen-storage materials for mobile applications. Nature 414, 353–358 (2001).

  2. 2

    Grochala, W. & Edwards, P. P. Thermal decomposition of the non-interstitial hydrides for the storage and production of hydrogen. Chem. Rev. 104, 1283–1315 (2004).

  3. 3

    Shore, S. G. & Parry, R. W. The crystalline compound ammonia-borane, H3NBH3 . J. Am. Chem. Soc. 77, 6084–6085 (1955).

  4. 4

    Stowe, A. C., Shaw, W. J., Linehan, J. C., Schmid, B. & Autrey, T. In situ solid state 11B MAS-NMR studies of the thermal decomposition of ammonia borane: Mechanistic studies of the hydrogen release pathways from a solid state hydrogen storage material. Phys. Chem. Chem. Phys. 9, 1831–1836 (2007).

  5. 5

    Hu, M. G., Geanangel, R. A. & Wendlandt, W. W. The thermal decomposition of ammonia borane. Thermochim. Acta 23, 249–255 (1978).

  6. 6

    Sit, V., Geanangel, R. A. & Wendlandt, W. W. The thermal dissociation of NH3BH3 . Thermochim. Acta 113, 379–382 (1987).

  7. 7

    Wolf, G., Baumann, J., Baitalow, F. & Hoffmann, F. P. Calorimetric process monitoring of thermal decomposition of B–N–H compounds. Thermochim. Acta 343, 19–25 (2000).

  8. 8

    Baitalow, F., Baumann, J., Wolf, G., Jaenicke-Rößler, K. & Leitner, G. Thermal decomposition of B–N–H compounds investigated by using combined thermoanalytical methods. Thermochim. Acta 391, 159–168 (2002).

  9. 9

    Gutowska, A. et al. Nanoscaffold mediates hydrogen release and the reactivity of ammonia borane. Angew. Chem. Int. Edn 44, 3578–3582 (2005).

  10. 10

    Denney, M. C., Pons, V., Hebden, T. J., Heinekey, M. & Goldberg, K. I. Efficient catalysis of ammonia borane dehydrogenation. J. Am. Chem. Soc. 128, 12048–12049 (2006).

  11. 11

    Bluhm, M. E., Bradley, M. G., Butterick, R., Kusari, U. & Sneddon, L. G. Amineborane-based chemical hydrogen storage: Enhanced ammonia borane dehydrogenation in ionic liquids. J. Am. Chem. Soc. 128, 7748–7749 (2006).

  12. 12

    Keaton, R. J., Blacquiere, J. M. & Baker, R. T. Base metal catalyzed dehydrogenation of ammonia-borane for chemical hydrogen storage. J. Am. Chem. Soc. 129, 1844–1845 (2007).

  13. 13

    Clark, T. J., Lee, K. & Manners, I. Transition-metal-catalyzed dehydrocoupling: A convenient route to bonds between main-group elements. Chem. Eur. J. 12, 8634–8648 (2006).

  14. 14

    Feaver, A. et al. Coherent carbon cryogel-ammonia borane nanocomposities for H-2 storage. J. Phys. Chem. B 111, 7469–7472 (2007).

  15. 15

    Myers, A. G., Yang, B. H. & Kopecky, D. J. Lithium amidotrihydroborate, a powerful new reductant. Transformation of tertiary amides to primary alcohols. Tetrahedron Lett. 37, 3623–3626 (1996).

  16. 16

    Schlesinger, H. I. & Burg, A. B. Hydrides of boron. VIII. The structure of the diammoniate of diborane and its relation to the structure of diborane. J. Am. Chem. Soc. 60, 290–299 (1938).

  17. 17

    David, W. I. F., Shankland, K. & Shankland, N. Routine determination of molecular crystal structures from powder diffraction data. Chem. Commun. 8, 931–932 (1998).

  18. 18

    Armstrong, D. R., Perkins, P. G. & Walker, G. T. The electronic structure of the monomers, dimers, a trimer, the oxides and the borane complexes of the lithiated ammonias. THEOCHEM-J. Mol. Struct. 122, 189–203 (1985).

  19. 19

    Gervais, C. et al. B-11 and N-15 solid state NMR investigation of a boron nitride preceramic polymer prepared by ammonolysis of borazine. J. Eur. Ceram. Soc. 25, 129–135 (2005).

  20. 20

    Chen, P., Xiong, Z. T., Luo, J. Z., Lin, J. Y. & Tan, K. L. Interaction of hydrogen with metal nitrides and imides. Nature 420, 302–304 (2002).

  21. 21

    Chen, P., Xiong, Z. T., Luo, J. Z., Lin, J. Y. & Tan, K. L. Interaction between lithium amide and lithium hydride. J. Phys. Chem. B 107, 10967–10970 (2003).

  22. 22

    Chater, P. A., David, W. I. F., Johnson, S. R., Edwards, P. P. & Anderson, P. A. Synthesis and crystal structure of Li4BH4(NH2)3 . Chem. Commun. 23, 2439–2441 (2006).

  23. 23

    David, W. I. F. et al. A Mechanism for non-stoichiometry in the lithium amide/lithium imide hydrogen storage reaction. J. Am. Chem. Soc. 129, 1594–1601 (2007).

  24. 24

    Chen, P., Xiong, Z. T., Yang, L. F., Wu, G. T. & Luo, W. F. Mechanistic investigations on the heterogeneous solid-state reaction of magnesium amides and lithium hydrides. J. Phys. Chem. B 110, 14221–14225 (2006).

Download references


P.C., Z.X. and G.W. are grateful for the financial support from A*STAR, Singapore, and helpful discussions with T. Kemmitt and M. Bowden from IRL and L. Sneddon from Univ. Pennsylvania. T.A., W.S. and A.K. would like to thank the DOE Center of Excellence in Chemical Hydrogen Storage for support. M.O.J., S.J. and P.E. would like to thank the EPSRC (SUPERGEN) for financial support. We wish to thank A. Fitch, M. Brunelli and I. Margiolaki for assistance in using the high-resolution beamline ID31 at the ESRF, Grenoble (France). A portion of the research described here was carried out in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the US Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. This work was carried out as a collaboration established by the IPHE project ‘Combination of Amine Boranes with MgH2 & LiNH2 for High Capacity Reversible Hydrogen Storage’.

Author information

Correspondence to Ping Chen.

Supplementary information

Supplementary Information

Supplementary information and figures S1-S4 (PDF 315 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Xiong, Z., Yong, C., Wu, G. et al. High-capacity hydrogen storage in lithium and sodium amidoboranes. Nature Mater 7, 138–141 (2008). https://doi.org/10.1038/nmat2081

Download citation

Further reading