高压复合储氢罐用储氢材料的研究进展

doi:10.11896/cldb.201901013

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Abstract Hydrogen energy is one of the most important choices for realizing clean energy because of its wide sources, no pollution, and high energy density. The technological innovation of fuel cells contributes to the attractive prospect of hydrogen energy in vehicles, but the problem of hydrogen filling and hydrogen storage has become one of the obstacles to the development of hydrogen energy cars. The safe and efficient hydrogen storage is crucial for the large-scale application of hydrogen energy.
Till now there have been developed three main hydrogen storage methods, which include high-pressure gaseous hydrogen storage, low-temperature liquid hydrogen storage and solid-state hydrogen storage. The gravimetric density of gaseous hydrogen storage system can be promoted by increasing the pressure of hydrogen and the specific strength of container material. However, H₂ molecular interaction causes a relatively low volumetric density of gaseous hydrogen storage system, and excessively high hydrogen pressure challenges the safety and heightens design difficulty and cost of hydrogen tanks. The liquid hydrogen storage owns ideal gravimetric and volumetric density, which can be realized by compres-sing and liquefying hydrogen gas. However, liquid hydrogen is particularly prone to volatilize and liquid hydrogen container requires strict storing conditions. In addition, the liquefying process of gaseous hydrogen is uneconomical, as it consumes an energy quantity that constitutes about 40% of the combustion heat release of the stored hydrogen. For the solid-state hydrogen storage, hydrogen is stored in the hydrides in the form of atom or ion. Hence, the solid-state hydrogen storage obtains an impressively high volumetric density and enjoys greater security because the hydrogen storage materials absorb/desorb hydrogen at mild conditions. But the gravimetric density of hydrogen storage materials is comparatively low. The high-pressure hybrid hydrogen storage vessel, which combines the advantages of gaseous and solid-state hydrogen storage methods, offers a feasible path to safe and high-density hydrogen storage. The volumetric density of high-pressure hydrogen tank can be effectively enhanced by the hydrogen storage materials, resulting in lower operating pressure, smaller volume, and higher safety. The performance promotion of the high-pressure hybrid hydrogen storage vessels depends upon the development of materials with excellent hydrogen sorption performances under high hydrogen pressure.
The AB₂ type ZrFe₂-based and TiCr₂ based alloys are the currently prevailing high-pressure hydrogen storage materials. Though researchers mainly concentrate on and have achieved the regulation of storage capacity, absorption/desorption pressure plateau and kinetics through the alloying trials which partially substitute elements with various atomic radius and electronic structures for either A-site or B-site, the gravimetric densities of ZrFe₂-based and TiCr₂-based alloys are still unsatisfactory. NaAlH₄ and AlH₃ display considerable potential as candidate storage materials owing to their intrinsically high storage density. For NaAlH₄, sufficient works have preliminarily confirmed the effectiveness of nanosizing and catalyst-doping toward dehydrogenation temperature reduction and cyclic stability enhancement. And the yield of AlH₃ along with its crystallinity can likely be enhanced by adopting ball milling or improving the solvent.
This review starts with a brief introduction of how the high-pressure hybrid hydrogen storage vessel works and a summary of the performance requirements of the hydrogen storage materials. It then provides detailed discussion and description upon the structure, characteristics and research status quo with respect to the above-mentioned two species of high-pressure hydrogen storage materials, i.e.hydrogen storage alloys (ZrFe₂, TiCr₂) and aluminum based complex hydrides (NaAlH₄, AlH₃).

Key words： solid-state hydrogen storage high-pressure hybrid hydrogen storage vessel high-pressure hydrogen storage material ZrFe₂ TiCr₂

Published: 24 January 2019

CLC number:

TG139+.7

Fund:This work was financially supported by the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (51621001) and National Natural Science Foundation of China (U1601212).

About author:: Chao Zhou received his B.E. degree in Nanjing Tech University in 2016. He is currently a graduate student in the School of Materials Science and Engineering, South China University of Technology, under the guidance of Professor Min Zhu. His research field is the composition design and performance regulation of hydrogen storage alloys.Min Zhu received his B.E., M.E. and Ph.D. degrees in Dalian university of technology in 1982, 1985 and 1988. He is now the vice president of South China University of Technology. He is also the professor and doctoral supervisor of the School of Materials Science and Engineering. Professor Min Zhu is the head of the National Excellent Course of Mechanical Engineering Materials. His main research areas include hydrogen sto-
rage materials, lithium ion battery electrode materials, mechanical alloying and nano metal materials, alloy phase transitions and shape memory alloys. He has published more than 250 papers in international academic journals such as Nature Commun.、 Angew. Chemie Int. Ed.、 Energy @ Environ Sci.、 Adv Mater.、 Materials Today、 Nano Energy、 Acta Mater.、 Appl. Phys. Lett.、 J. Mater. Chem、 J. Alloys & Compounds、 Metall. Mater. Trans.、 Scr. Mater. as a first or correspondent author

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Cite this article:

ZHOU Chao,WANG Hui,OUYANG Liuzhang, et al. The State of the Art of Hydrogen Storage Materials for High-pressure Hybrid Hydrogen Vessel[J]. Materials Reports, 2019, 33(1): 117-126.

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http://www.mater-rep.com/EN/10.11896/cldb.201901013 OR http://www.mater-rep.com/EN/Y2019/V33/I1/117

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