Superior Reversible Hydrogen Storage of the LiBH4 + MgH2 system

Significance 

Hydrogen storage is the tailback for the implementation of a so-called “hydrogen economy”, which could replace the fossil fuels used today with hydrogen generated by renewable energy. Lithium borohydride (LiBH4) is a promising hydrogen storage material for some applications. In 2003, a study was published that hypothesized the theoretical hydrogen storage capacity of a mixture of LiBH4 and MgH2 (magnesium hydride) at 11.45 wt % H2 at certain temperature. It is rather unfortunate that since that discovery, there have been few studies on the dehydrogenation and rehydrogenation of LiBH4 + MgH2 system below the melting point of LiBH4 (275 °C). Of the few available publications, a recent study has shown that nano-LiBH4 + nano-MgH2 mixture produced from ball milling with aerosol spraying (BMAS) can release 4.11 wt % H2 in the first dehydrogenation at a temperature ≤265 °C.

All factors considered, the prospects of LiBH4 + MgH2 mixture has been limited by its sluggish kinetics despite its excellent hydrogen storage capacity theoretically. To address this, researchers from the Department of Mechanical, Materials and Aerospace Engineering at Illinois Institute of Technology: Dr. Zhao Ding and Professor Leon Shaw evaluated the superior hydrogen release behavior of the solid-state BMAS powder with 50% LiBH4 from the viewpoints of both thermodynamics and chemical kinetics. Their goal was to demonstrate that the BMAS approach recently presented could not only tune the thermodynamics but also improve the kinetics for hydrogen release from a LiBH4 + MgH2 mixture. Their work is currently published in the research journal, ACS Sustainable Chemistry & Engineering.

Given the significantly improved hydrogen storage capacity for the LiBH4 + MgH2 system obtained via BMAS, in-depth assessment of the background processes becomes a necessity to further improve on the entire system. As such, the two scholars evaluated the improved thermodynamics from the viewpoint of the significantly heightened dissociation pressure. In fact, the research pair used nine different kinetics models to analyze the solid-state dehydrogenation behavior of the BMAS powder with 50% LiBH4 at 265 °C.

The kinetics analysis revealed that the rate limiting step of this BMAS powder was initially controlled by the nucleation/growth process but then changed to moving-phase boundary control and finally to diffusion control as the number of dehydrogenation/rehydrogenation cycles increased. Moreover, thermal analysis results indicated that the apparent activation energy of the BMAS powder was reduced by 23.3 and 30.6 kJ/mol when compared to that of bulk LiBH4 and ball-milled MgH2 + C mixtures, respectively, thus revealing BMAS as an effective method to promote hydrogen release from LiBH4 + MgH2 mixtures.

In summary, the study by Dr. Zhao Ding and Professor Leon Shaw looked carefully on the unusually high hydrogen release through the solid-state BMAS powder with 50% LiBH4 at 265 °C from the viewpoints of the thermodynamic driving force, as well as the chemical kinetics of the dehydrogenation process. Remarkably, it was established that the dissociation pressures for the BMAS sample were ∼700 and ∼1910% higher than those of the commercial LiBH4 and commercial MgH2, respectively. In a statement to Advances in Engineering, Dr. Zhao Ding commented that the new insights in the solid-state dehydration kinetics and the associated reaction mechanisms established in their study could lay a scientific foundation for further understanding and improvements in enhancing the solid-state dehydrogenation/rehydrogenation properties of LiBH4 + MgH2 mixtures in the future.

Superior Reversible Hydrogen Storage of the LiBH4 + MgH2 system Enabled by High-Energy Ball Milling with In-situ Aerosol Spraying - Advances in Engineering

About the author

Dr. Zhao Ding carried out this research as part of his Ph.D. work in materials science and engineering from Illinois Institute of Technology, Chicago, Illinois, USA. He has long-term been engaged in the development and research of chemical and complex hydrides for novel hydrogen storage materials. Specifically, Dr. Ding has established a novel method, termed as Ball Milling with Aerosol Spraying (BMAS), to synthesize a nano-LiBH4 + nano-MgH2 mixture with superior reversible hydrogen storage properties, which opens up a new direction for investigating the hydrogen storage materials for fuel cell vehicles. Related research results has been published in the recent publication of the “Energy Storage Materials”, “Chemical Engineering Journal”, “Journal of Power Source” “ACS Sustainable Chemistry and Engineering”, “Journal of Alloys and Compounds” and “Nano Materials Science” magazines online. He received his Ph.D. degree in 2019 based on these works and will become a full-time professor in China in the near future.

About the author

Dr. Leon L. Shaw is Rowe Family Endowed Chair Professor in Sustainable Energy and Professor of Materials Science and Engineering at Illinois Institute of Technology (IIT), Chicago, USA. His main research interest is in nanomaterials synthesis and processing for energy storage and structural applications. In the energy storage arena, his research team has worked on hydrogen storage materials, anode and cathode materials for Li-ion batteries, Na-ion batteries, and hybrid redox flow batteries over the last decade. He has authored and co-authored more than 300 archival refereed publications with 9,600 plus non-self citations (according to Google Scholar). He is a Member of the EU Academy of Science, Member of the Connecticut Academy of Science and Engineering, Fellow of ASM International, and Fellow of the World Academy of Materials and Manufacturing Engineering.

Reference

Z. Ding, L. Shaw. Enhancement of Hydrogen Desorption from Nanocomposite Prepared by Ball Milling MgH2 with In Situ Aerosol Spraying LiBH4. ACS Sustainable Chemistry & Engineering 2019, volume7, page 15064−15072.

Go To ACS Sustainable Chemistry & Engineering 2019

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