Target complex Programme for Research of NAS UKRAINE

«Development of scientific bases for hydrogen production, storage and use in autonomous energy supply systems»

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Development of physicochemical principles for the creation of high-capacity hydride-forming materials and their use in stationary hydrogen storage systems and as electrodes for electrochemical energy systems

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The project is aimed to solve the problem of getting to the needs of the hydrogen energetics highly efficient hydrogen energy storage materials, namely that decompose at low temperatures and thus possess a combination of properties such as high hydrogen storage capacity and cyclic stability during rapid kinetics of sorption-desorption of hydrogen. Therefore, the aim of one of the project tasks is lowering thermal stability of hydride phases of Mg-based mechanical alloys by choice and optimization of the composition and conditions of their deriving as well as by their dispersion and mechanical alloying.

Fields of application

The hydrogen energetics is the main field of application of hydrogen-sorption materials developed during the project fulfillment. It is also expected using the developed hydrogen-sorption materials based on magnesium and its alloys in laboratory installations for thermal hydrogen desorption researches, in high-power modules of energy convertors and hydride heat pumps, etc.

Brief description

In the project part devoted to developing methods of deriving and improving the properties of hydrogen-sorption materials for hydrogen storage alloys based on magnesium, it is planned to carry out researches aimed at obtaining complex characteristics of these materials necessary for their practical application as hydrogen batteries and in the first place, fast kinetics and low temperature of full hydrogen release at a pressure 1 bar. To achieve the specified improving performance of the obtained materials, we plan to use new synthesis methods (mechanical and reactive mechanical alloying) as well as to involve processes of mechanical alloying and dispersion, which allow to change and generate needed hydrogen-sorption properties, required chemical state of their surfaces through effects on electronic and thermodynamic properties. Mechanical synthesis was carried out of magnesium-based alloys with different composition of alloying elements, in particularly Mg-Si-Ti-Fe(Ni) alloys. The optimal composition of alloys and their synthesis conditions providing improved complex of specified essential characteristics was determined.

Expected properties

Results of the project studies of the effect of different alloying elements and different synthesis conditions on hydrogen-sorption properties, thermal stability and kinetics of hydrogen desorption process of mechanical alloy composites based on Mg enable improved mechanical-chemical methods used to obtain materials for hydrogen storage and to optimize conditions of their synthesis. The results will improve a number of characteristics of practice needs (hydrogen capacity and cyclic stability, kinetics of hydrogen sorption-desorption, thermal stability and decomposition temperature of the hydride phase).

Advantages

It has been established that mechanical alloying of Mg by Al-Fe, Al-Ti gives best hydrogen-sorption characteristics and kinetics of hydrogen desorption from MgH2 hydride phase in comparison with that alloying by Fe. As a result of reactive milling 10 h the mixtures Mg +(10 wt%. Al + 10 wt.% Ti) ; Mg +(10 wt%. Al +10 wt.% Ni), we have achieved bigger value of hydrogen capacity:6.57 wt.% H2, 5.57 wt.% H2. After reactive milling 20 h we have achieved of hydrogen capacity 5.58 wt.% H2. Temperature of the beginning of 1-st H2 desorption was 260 0C (PH2 = 1 bar). It has been established that the addition of Si, Ti, Fe to magnesium leads to significant 6 times improvement in kinetics of hydrogen desorption from the hydride phase MgH2 .

Competitor

Department Mater.Scien.&Engineer.ZhejiangUniversity,China
Department Mater.Univer London, UK
Course in Materials Science &Chemistry, Tokai University, Numazu, Japan
Institute for Energy Technology, P.O. Box 40, N-2027 Kjeller, Norway.

Stage of development

We have determined the effect of lowering the temperature and improving the kinetics of H2 desorption from MgH2 hydride phase of the alloy obtained by reactive milling through mechanical alloying of Al and Ti, Al and Fe, Al and Ni of magnesium in the process of milling in a hydrogen atmosphere. We have also studied contribution to reducing thermal stability and decomposition temperature of MgH2 hydride phase of the mechanical alloys Mg +(Si-Ti-Fe) that was synthesized under different conditions of hydrogenation. The results indicate that our studies allow choosing the composition of alloying elements and conditions of synthesis of mechanical alloys that provide maximum heat resistance and low decomposition temperature of MgH2 while improving the kinetics of hydrogen sorption/desorption.

Intellectual property

Publications on results carried out within the project:

  • Ershova O.G., Dobrovolsky V.D., SoloninY. M., Khyzhun O.Yu, Koval A.Yu. The effect of Al on thermal stability and kinetics of decomposition of MgH2 prepared by mechanochemical reaction at different conditions // Materials Chemistry and Physics. – 2015. – 162. – p.408 – 416.

  • Dobrovolsky V.D., Ershova O.G., Solonin Yu. M., Khyzhun O.Y. Influence of titanium and iron additives to magnesium upon hydrogen-sorption properties, thermal stability and kinetics of hydrogen desorption from MgH2 phase of mechanical alloy // Powder Metallurgy & Metal Ceramics, 2016, No. 7-8, P. 124-137.

  • Dobrovolsky V.D., Ershova O.G., Solonin Yu. M. Thermal Resistance and the Kinetics of Hydrogen Desorption from Hydrides of the Mg–Al–Ni–Ti Mechanical Alloy // Materials Science. – 2016. - 51(4), 457-464.

  • V.D. Dobrovolsky, O.Y. Khyzhun, A.K. Sinelnichenko, O.G. Ershova,Y.M. Solonin. XPS study of influence of exposure to air on thermal stability and kinetics of hydrogen decomposition of MgH2 films obtained by direct hydrogenation from gaseous phase of metallic // Journal of Electron Spectroscopy and Related Phenomena.- 2017.- 215, p. 28-35.

  • Valentin Davidovich Dobrovolsky, Olga Georgievna Ershova, Yuriy Michailovich Solonin. Alloying effect of Ti, Fe, Ni and Al on hydrogen desorption behavior of MgH2 synthesized by reactive mechanical alloying. // Innovations in Corrosion and Materials Science. -2017. – v. 7. – p. 1-15.

  • Ershova O.G., Dobrovolsky V.D., Solonin Y.M. Mechanical alloys Mg-Me (Me: Ti, Fe, Ni, Al) & Mg -Me1-Me2 (Ìå1: Al; Me2: Ti, Fe, Ni) with low resistance and improved kinetics of hydrogenation /dehydrogenation for hydrogen storage applications // French-Ukrainia Journal of Chemistry. 2018. –v. 6. – isse 1. – p. 31-55.

  • Dobrovolsky V.D., Ershova O.G., Solonin Yu. M. Magnesium-based composites obtained by reactive mechanical alloying for hydrogen storage systems // Materials Science: Achievements and Prospects. In 2 tons. T1.- Kiev: Academperiodika. - 2018. – p. 174-194.

  • O.G. Ershova, V.D. Dobrovolsky, Yu.M. Solonin, A.Yu.Koval Hydrogen sorption properties, thermal stability and kinetics of hydrogen desorption from the hydride phase of the MgH2 of a mechanical alloy of magnesium with Ti and Y//Met.Phys.and Novel Tech. – 1029. –v.41(8). – p.981-1001.

    • Contact information

    Institute- Executor: Frantsevych Institute for Problems of Materials Science of National Academy of Sciences of Ukraine

    Project leader:

    Ershova Olga G.

    candidate of Technical Sciences
    Senior Researcher

    Tel. +380 44 205-79-27

    E-mail: dobersh2017@ukr.net
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