Review Article
Recent advances in magnesium-based hydrogen storage materials with multiple catalysts

https://doi.org/10.1016/j.ijhydene.2019.02.237Get rights and content

Highlights

  • Approaches of producing Mg composites with multiple catalysts were summarized.

  • Mg-based hydrogen storage materials with multiple catalysts were reviewed.

  • Catalytic mechanism of the multiple catalysts was analyzed.

  • Possible future research directions in multiple catalysts system were provided.

Abstract

The slow hydrogenation/dehydrogenation kinetics and high thermodynamic stability of Mgsingle bondH bond are the two major limitations for large-scale utilization of MgH2. Constructing Mg nanoparticles (NPs) with large specific surface area and short hydrogen diffusion distance and adding effective catalysts to facilitate the sorption kinetics are the main ways to solve the remained shortages of Mg/MgH2 system. This article reviews the recent advances in the Mg-based nanocomposites with multiple catalysts produced by different approaches. The multiple catalysts was classified into transition metals and/or their hydrides (TM and/or TMH), TM together with metal oxides, TM and/or TMH together with metal hadlies, TM and/or TMH together with metal sulfides, TM and/or TMH together with Mg2M and other multiple catalysts systems. Compared with single catalyst, the multiple catalysts display enhanced synergistic catalytic effects on the hydrogen absorption and desorption rates.

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Recent advances in Mg-based hydrogen materials with different multiple catalysts and their catalytic mechanisms were reviewed.

Introduction

Over the past decades, traditional fossil fuels such as gasoline, coal, kerosene and diesel oil et al. are excessively consumed, leaving the shortage of fossil fuels and various worldwide problems that threatens survival of mankind. Thus, developing renewable energy sources (hydrogen, solar, wind and geothermal) to replace the fossil fuels has been becoming strategic issues for countries all over the world. Compared with the various renewable energy sources, hydrogen is clean and easy to converse with electricity. Moreover, various methods can be used to obtain hydrogen, such as hydrogen generation by hydrolysis and water electrolysis. These advantages make hydrogen a considerable media for energy carrier material used for fuel cell-driven portable, mobile, and stationary applications. However, developing a safe, effective and economical way to storage the hydrogen is the major limitation to broaden the usage of hydrogen energy [1]. As we all know the two traditional storage ways of high-pressed hydrogen gas and cryogenic hydrogen liquid can not meet the US Department of Energy (DOE) target for their shortages of energy-extensive consumption, insecurity, low hydrogen storage capacity and high cost [2]. Comparatively, metal hydride materials show great potential to meet the ultimate DOE target for its essential characteristics of high volumetric and gravimetric capacity and safety. Researchers have studied many hydrogen storage materials and some of them are already used in application, such as rare earth metal La-based alloy [3], Ti-based alloy [4], nitrogen hydride [5], alanates [6], amides [7] and borohydrides [8]. However, none of the materials mentioned above can satisfy all the necessary requirements for one or more drawbacks, including high cost, high operation temperature, low reversibility, sluggish hydrogen sorption kinetics, and release of undesirable by-products. Elemental hydride MgH2 is considered to be the most attractive material for onboard hydrogen storage with advantages of possessing high theoretical gravimetric capacity of 7.6 wt%, high energy density of 9 MJ kg−1, abundance on earth, reversibility and low cost [1].

Section snippets

Methods to modify the hydrogen storage properties of Mg/MgH2 system

Although Mg possesses considerable advantages mentioned above, the practical application of Mg is still hindered by its sluggish hydrogen desorption kinetics and thermodynamically stable of the Mgsingle bondH bond, leading to the high operating temperature (above 473 K) and hydrogen pressure (at least 3 MPa) to achieve an adequate hydrogenation/dehydrogenation rates [9]. Jongh [10] reported that the main rate-limiting factor of the hydrogen absorption process was the dissociation of hydrogen molecule at

High energy ball milling

Compared with other approaches, high energy ball milling (HEBM) is the most common method to disperse different catalysts in Mg/MgH2 systems. The composition of the composites, including concentrations and types of the catalysts, can be easily designed though the particle size is still in the range of micrometers [76]. The defects and the large surface of the catalysts and Mg particles produced during the ball milling process can serve as speculative pathways for the hydrogen diffusion and

Transition metals and/or their hydrides(TM and/or TMH)

Transition metals and/or transition metals hydrides are the most universal catalysts used for enhancing the hydrogen storage properties of Mg. In transition metals multiple catalysts system, most metals particles except Cr, Mo would change to hydrides or Mg2M alloys (M = Ni,Co,Fe,Cu,Zn) during the hydrogen absorption and desorption process. Therefore, the transition metal multiple catalysts mainly exist in multilayer thin films, in which the phase changes of the transition metal layers would

Conclusions and perspectives

Mg-based material is a potential candidate for hydrogen storage to boom the hydrogen economy due to its various prominent virtues. The main issues of Mg-based materials mainly include poor kinetics and high operation temperatures. Doping multiple catalysts into Mg system is an easy way to modify the drawbacks of Mg-based materials. Different multiple catalysts with different introducing methods display different structures such as core/shell, particle decoration and plates, and the multiple

Acknowledgements

The authors acknowledge the support of this work by the Joint Fund of the National Natural Science Foundation of China and Baosteel Group Corporation (No. U1560106), the Aeronautical Science Foundation of China (No.2016ZF51050), the National Natural Science Foundation of China (No. 51731002), the Scientific Research Foundation for the Returned Overseas Chinese Scholars (State Education Ministry) and the Academic Excellence Foundation of BUAA for PhD Students.

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