Journal of Materials Science

, Volume 55, Issue 5, pp 1959–1972 | Cite as

Modifying effects and mechanisms of graphene on dehydrogenation properties of sodium borohydride

  • Y. Fang
  • J. ZhangEmail author
  • M. Y. Hua
  • D. W. Zhou
Chemical routes to materials


Sodium borohydride (NaBH4) is a promising solid-state hydrogen storage material because of its low toxicity, high environmental stability and release of high-purity hydrogen. Nevertheless, the practical application of NaBH4 is still hampered by its high desorption temperature and slow hydrogen exchange kinetics. Using experimental and first-principles calculations approaches, the dehydrogenation properties and modifying mechanisms of NaBH4+10 wt%graphene composite acquired by ball-milling are systematically investigated in this work. The results show that the graphene plays a cooperative catalysis–confinement effect on NaBH4. X-ray diffraction analysis displays that no new phases formed due to the mutual inertia between NaBH4 and graphene during ball-milling. Scanning electron microscopy and transmission electron microscopy observations show that the NaBH4 particles are significantly refined after graphene addition, which effectively restrains the agglomeration of NaBH4 particles. Thermogravimetry testing and mass spectrometry testing indicate that the onset dehydrogenation temperature of the NaBH4+10 wt%graphene composite is decreased by about 114 °C relative to the milled pristine NaBH4. First-principles calculations reveal that the enhanced dehydrogenation properties of NaBH4 after graphene addition should be ascribed to the reduced dehydrogenation enthalpy of NaBH4 and strong binding energy between NaBH4 and graphene as well as the electron transfer from NaBH4 to graphene.



This work was supported by the National Natural Science Foundation of China (Nos. 51874049 and 51401036), the Hunan Provincial Natural Science Foundation of China (Nos. 2017JJ2263 and 2018JJ2426), the Research and Innovation Project of Graduate Students in Hunan Province (No. CX20190675) and the “Double First-Class” Scientific Research International Cooperation and Development Project of Changsha University of Science and Technology (2018IC02).


  1. 1.
    Schlapbach L, Züttel A (2001) Hydrogen-storage materials for mobile applications. Nature 414:353–358Google Scholar
  2. 2.
    Jain IP (2009) Hydrogen the fuel for 21st century. Int J Hydrogen Energy 34:7368–7378Google Scholar
  3. 3.
    Sakintuna B, Lamari-Darkrim F, Hirscher M (2007) Metal hydride materials for solid hydrogen storage: a review. Int J Hydrogen Energy 32:1121–1140Google Scholar
  4. 4.
    Zhang J, Huang YN, Mao C, Peng P (2012) Synergistic effect of Ti and F co-doping on dehydrogenation properties of MgH2 from first-principles calculations. Int J Hydrogen Energy 538:205–211Google Scholar
  5. 5.
    Zhang J, Qu H, Yan S, Wu G, Yu XF, Peng P (2017) Enhanced hydrogen diffusion in magnesium based hydride induced by strain and doping from first principle study. J Alloys Compd 694:687–693Google Scholar
  6. 6.
    Zhang J, Yan S, Yu LP, Zhou XJ, Zhou T, Peng P (2018) Enhanced hydrogen storage properties and mechanisms of magnesium hydride modified by transition metal dissolved magnesium oxides. Int J Hydrogen Energy 43:21864–21873Google Scholar
  7. 7.
    Zhang J, Sun LQ, Zhou YC, Peng P (2015) Dehydrogenation thermodynamics of magnesium hydride doped with transition metals: experimental and theoretical studies. Comp Mater Sci 98:211–219Google Scholar
  8. 8.
    Ding ZM, Ma YF, Peng DD, Zhang L, Zhao YM, Li Y, Han SM (2018) Effects of the hierarchical pyrolysis polyaniline on reversible hydrogen storage of LiBH4. Prog Nat Sci 28:529–533Google Scholar
  9. 9.
    He Z, Liu HZ, Gao SC, Wang XH (2018) Enhanced dehydrogenation kinetic properties and hydrogen storage reversibility of LiBH4 confined in activated charcoal. Trans Nonferr Metal Soc 28:1618–1625Google Scholar
  10. 10.
    Liu HZ, Xu L, Sheng P, Liu SY, Zhao GY, Wang B, Wang XH, Yan M (2017) Hydrogen desorption kinetics of the destabilized LiBH4-AlH3 composites. Int J Hydrogen Energy 42:22358–22365Google Scholar
  11. 11.
    Jiang Z, Yuan JG, Han HQ, Wu Y (2018) Effect of carbon nanotubes on the microstructural evolution and hydrogen storage properties of Mg(BH4)2. J Alloys Compd 743:11–16Google Scholar
  12. 12.
    Saldan I, Frommen C, Llamas-Jansa I, Kalantzopoulos GN, Hino S, Arstad B, Heyn RH, Zavorotynska O, Deledda S, Sørby MH, Fjellvåg H, Hauback BC (2015) Hydrogen storage properties of γ–Mg (BH4)2 modified by MoO3 and TiO2. Int J Hydrogen Energy 40:12286–12293Google Scholar
  13. 13.
    Møller KT, Grinderslev JB, Jensen TR (2017) A NaAlH4-Ca(BH4)2 composite system for hydrogen storage. J Alloys Compd 720:497–501Google Scholar
  14. 14.
    Mustafa NS, Yap FAH, Yahya MS, Ismail M (2018) The hydrogen storage properties and reaction mechanism of the NaAlH4 + Ca(BH4)2 composite system. Int J Hydrogen Energy 43:11132–11140Google Scholar
  15. 15.
    Orimo S, Nakamori Y, Eliseo JR, Züttel A, Jensen CM (2007) Complex hydrides for hydrogen storage. Chem Rev 107:4111–4132Google Scholar
  16. 16.
    Ahluwalia RK, Hua TQ, Peng JK (2012) On-board and off-board performance of hydrogen storage options for light-duty vehicles. Int J Hydrogen Energy 37:2891–2910Google Scholar
  17. 17.
    Zhong H, Ouyang LZ, Ye JS, Liu WJ, Wang H, Yao XD, Zhu M (2017) An one-step approach towards hydrogen production and storage through regeneration of NaBH4. Energy Storage Mater 7:222–228Google Scholar
  18. 18.
    Mao JF, Gu QF, Guo ZP, Liu HK (2015) Sodium borohydride hydrazinates: synthesis, crystal structures, and thermal decomposition behavior. J Mater Chem A 3:11269–11276Google Scholar
  19. 19.
    Mao JF, Gregory DH (2015) Recent advances in the use of sodium borohydride as a solid state hydrogen store. Energies 8:430–453Google Scholar
  20. 20.
    Wu C, Bai Y, Yang JH, Wu F, Long F (2012) Characterizations of composite NaNH2–NaBH4 hydrogen storage materials synthesized via ball milling. Int J Hydrogen Energy 37:889–893Google Scholar
  21. 21.
    Javadian P, Sheppard DA, Buckley CE, Jensen TR (2015) Hydrogen storage properties of nanoconfined LiBH4–NaBH4. Int J Hydrogen Energy 40:14916–14924Google Scholar
  22. 22.
    Pei ZW, Wu C, Bai Y, Liu X, Wu F (2017) NaNH2–NaBH4 hydrogen storage composite materials synthesized via liquid phase ball-milling: influence of Co–Ni–B catalyst on the dehydrogenation performances. Int J Hydrogen Energy 42:14725–14733Google Scholar
  23. 23.
    Lee J, Shin H, Choi KS, Lee J, Choi JY, Yu HK (2019) Carbon layer supported nickel catalyst for sodium borohydride (NaBH4) dehydrogenation. Int J Hydrogen Energy 44:2943–2950Google Scholar
  24. 24.
    Kao HY, Lin CC, Hung CJ, Hu CC (2018) Kinetics of hydrogen generation on NaBH4 powders using cobalt catalysts. J Taiwan Inst Chem E 87:123–130Google Scholar
  25. 25.
    Ali NA, Yahya MS, Mustafa NS, Sazelee NA, Idris NH, Ismail M (2019) Modifying the hydrogen storage performances of NaBH4 by catalyzing with MgFe2O4 synthesized via hydrothermal method. Int J Hydrogen Energy 44:6720–6727. CrossRefGoogle Scholar
  26. 26.
    Zheng XP, Zheng JJ, Liu SL, Qu XH, Li P, Gao YB, Luo WH (2015) A new solid material for hydrogen storage. Int J Hydrogen Energy 40:10502–10507Google Scholar
  27. 27.
    De Jongh PE, Adelhelm P (2010) Nanosizing and nanoconfinement: new strategies towards meeting hydrogen storage goals. Chem Sus Chem 3:1332–1348Google Scholar
  28. 28.
    Pang YP, Liu YF, Gao MX, Ouyang LZ, Liu JW, Wang H, Zhu M, Pan H (2014) A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures. Nat Commun 5:3519Google Scholar
  29. 29.
    House SD, Liu XF, Rockett AA, Majzoub EH, Robertson IM (2014) Characterization of the dehydrogenation process of LiBH4 confined in nanoporous carbon. J Phys Chem C 118:8843–8851Google Scholar
  30. 30.
    Carr CL, Majzoub EH (2016) Surface-functionalized nanoporous carbons for kinetically stabilized complex hydrides through lewis acid-lewis base chemistry. J Phys Chem C 120:11426–11432Google Scholar
  31. 31.
    Rueda M, Sanz-Moral LM, Martín Á (2018) Innovative methods to enhance the properties of solid hydrogen storage materials based on hydrides through nanoconfinement: a review. J Supercrit Fluid 141:198–217Google Scholar
  32. 32.
    Ampoumogli A, Steriotis T, Trikalitis P, Giasafaki D, Bardaji EG, Fichtner M, Charalambopoulou G (2011) Nanostructured composites of mesoporous carbons and boranates as hydrogen storage materials. J Alloys Compd 509:S705–S708Google Scholar
  33. 33.
    Ngene P, van den Berg R, Verkuijlen MHW, de Jong KP, de Jongh PE (2011) Reversibility of the hydrogen desorption from NaBH4 by confinement in nanoporous carbon. Energy Environ Sci 4:4108–4115Google Scholar
  34. 34.
    Wang FH, Zhang YJ, Wang YN, Luo YM, Chen YN, Zhu H (2018) Co-P nanoparticles supported on dandelion-like CNTs-Ni foam composite carrier as a novel catalyst for hydrogen generation from NaBH4 methanolysis. Int J Hydrogen Energy 43:8805–8814Google Scholar
  35. 35.
    Chen B, Chen SJ, Bandal HA, Appiah-Ntiamoah R, Jadhav AR, Kim H (2018) Cobalt nanoparticles supported on magnetic core-shell structured carbon as a highly efficient catalyst for hydrogen generation from NaBH4 hydrolysis. Int J Hydrogen Energy 43:9296–9306Google Scholar
  36. 36.
    Yang H, Lombardo L, Luo W, Kim W, Züttel A (2018) Hydrogen storage properties of various carbon supported NaBH4 prepared via metathesis. Int J Hydrogen Energy 43:7108–7116Google Scholar
  37. 37.
    Barghi SH, Tsotsis TT, Sahimi M (2014) Chemisorption, physisorption and hysteresis during hydrogen storage in carbon nanotubes. Int J Hydrogen Energy 39:1390–1397Google Scholar
  38. 38.
    Ariharan A, Viswanathan B, Nandhakumar V (2016) Hydrogen storage on boron substituted carbon materials. Int J Hydrogen Energy 41:3527–3536Google Scholar
  39. 39.
    Chong L, Zeng XQ, Ding WJ, Liu DJ, Zou JX (2015) NaBH4 in “graphene wrapper:” significantly enhanced hydrogen storage capacity and regenerability through nanoencapsulation. Adv Mater 27:5070–5074Google Scholar
  40. 40.
    Delley B (2000) From molecules to solids with the DMol3 approach. J Chem Phys 113:7756–7764Google Scholar
  41. 41.
    Perdew JP, Wang Y (1992) Accurate and simple analytic representation of the electron-gas correlation energy. Phys Rev B 45:13244Google Scholar
  42. 42.
    Perdew JP, Chevary JA, Vosko SH, Jackson KA, Pederson MR, Singh DJ, Fiolhais C (1992) Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys Rev B 46:6671–6687Google Scholar
  43. 43.
    Delley B (2000) DMol3 DFT studies: from molecules and molecular environments to surfaces and solids. Comput Mater Sci 17:122–126Google Scholar
  44. 44.
    Monkhorst HJ, Pack JD (1976) Special points for Brillouin-zone integrations. Phys Rev B 13:5188–5192Google Scholar
  45. 45.
    Kumar S, Jain A, Miyaoka H, Ichikawa T, Kojima Y (2017) Study on the thermal decomposition of NaBH4 catalyzed by ZrCl4. Int J Hydrogen Energy 42:22432–22437Google Scholar
  46. 46.
    Gong L, Liu YZ, Liu FY, Jiang LX (2017) Room-temperature deposition of flexible transparent conductive Ga-doped ZnO thin films by magnetron sputtering on polymer substrates. J Mater Sci Mater Electron 28:6093–6098Google Scholar
  47. 47.
    Gong L, Lu J, Ye Z (2013) Study on the structural, electrical, optical, adhesive properties and stability of Ga-doped ZnO transparent conductive films deposited on polymer substrates at room temperature. J Mater Sci Mater Electron 24:148–152Google Scholar
  48. 48.
    Zhang J, Qu H, Wu G, Song LB, Yu XF, Zhou DW (2016) Remarkably enhanced dehydrogenation properties and mechanisms of MgH2 by sequential-doping of nickel and graphene. Int J Hydrogen Energy 41:17433–17441Google Scholar
  49. 49.
    Du Q, Li SM, Huang GW, Feng QP (2017) Enhanced electrochemical kinetics of magnesium-based hydrogen storage alloy by mechanical milling with graphite. Int J Hydrogen Energy 42:21871–21879Google Scholar
  50. 50.
    Gao SC, Liu HZ, Xu L, Li SQ, Wang XH, Yan M (2018) Hydrogen storage properties of nano-CoB/CNTs catalyzed MgH2. J Alloys Compd 735:635–642Google Scholar
  51. 51.
    Zhang J, Yu XF, Mao C, Long CG, Chen J, Zhou DW (2015) Influences and mechanisms of graphene-doping on dehydrogenation properties of MgH2: experimental and first-principles studies. Energy 89:957–964Google Scholar
  52. 52.
    Ojani R, Valiollahi R, Raoof JB (2014) Au hollow nanospheres on graphene support as catalyst for sodium borohydride electrooxidation. Appl Surf Sci 311:245–251Google Scholar
  53. 53.
    Zhang J, Qu H, Yan S, Yin LR, Zhou DW (2017) Dehydrogenation properties and mechanisms of MgH2-NiCl2 and MgH2-NiCl2-graphene hydrogen storage composites. Met Mater Int 23:831–837Google Scholar
  54. 54.
    Xu J, Meng RR, Cao JY, Gu XF, Qi ZQ, Wang WC, Chen ZD (2013) Enhanced dehydrogenation and rehydrogenation properties of LiBH4 catalyzed by graphene. Int J Hydrogen Energy 38:2796–2803Google Scholar
  55. 55.
    Zhang J, Qu H, Yan S, Yin LR, Yu XF, Zhou DW (2017) Improved hydrogen desorption properties of MgH2 by graphite and NiF2 addition: experimental and first-principles investigations. J Mater Sci 52:8681–8689. CrossRefGoogle Scholar
  56. 56.
    Nale A, Pendolino F, Maddalena A, Colombo P (2016) Enhanced hydrogen release of metal borohydrides M(BH4)n (M = Li, Na, Mg, Ca) mixed with reduced graphene oxide. Int J Hydrogen Energy 41:11225–11231Google Scholar
  57. 57.
    Zhang J, Yan S, Qu H (2018) Recent progress in magnesium hydride modified through catalysis and nanoconfinement. Int J Hydrogen Energy 43:1545–1565Google Scholar
  58. 58.
    Zhang J, Qu H, Yan S, Wu G, Yu XF, Zhou DW (2017) Catalytic effect of nickel phthalocyanine on hydrogen storage properties of magnesium hydride: experimental and first-principles studies. Int J Hydrogen Energy 42:28485–28497Google Scholar
  59. 59.
    Chen XF, Wang LFZ, Zhang WT, Zhang JL, Yuan YQ (2017) Ca-decorated borophene as potential candidates for hydrogen storage: a first-principle study. Int J Hydrogen Energy 42:20036–20045Google Scholar
  60. 60.
    Wang LFZ, Chen XF, Du HY, Yuan YQ, Qu H, Zou M (2018) First-principles investigation on hydrogen storage performance of Li, Na and K decorated borophene. Appl Surf Sci 427:1030–1037Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Hunan Provincial Key Laboratory of Intelligent Manufacturing Technology for High-performance Mechanical EquipmentChangsha University of Science and TechnologyChangshaChina
  2. 2.State Key Laboratory of Advanced Design and Manufacturing for Vehicle BodyHunan UniversityChangshaChina

Personalised recommendations