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Hybrid Magnesium Based Materials for Hydrogen Energy Storage

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Hybrid Magnesium Based Materials for Hydrogen Energy Storage Hybrid Magnesium Based Materials for Hydrogen Energy Storage by Eki Jaya Sasmita Setijadi A thesis in fulfilment of the requirements for the degree of Doctor of Philosophy School of Chemical Engineering The University of New South Wales Sydney, Australia 2014 PLEASE TYPE THE UNIVERSITY OF NEW SOUTH WALES Thesis/Dissertation Sheet Surname or Family name: Setijadi First name: Eki Other name/s: Jaya Sasmita Abbreviation for degree as given in the University calendar: PhD School: Chemical Engineering Faculty: Engineering Title: Hybrid Magnesium Based Materials for Hydrogen Energy Storage Abstract 350 words maximum: (PLEASE TYPE) Nanostructuring metal hydride has been identified as a potential approach to overcome kinetics and thermodynamic limitations due to the large surface area and high surface energy of nanomaterials. However, in practice the synthesis of such nanosized materials with controlled properties is a real challenge. In particular, the high reactivity of magnesium - a promising material for hydrogen storage - challenges its synthesis at the nanoscale. Hence, this thesis aims to explore different strategies based on wet synthesis methods to synthesize and stabilize magnesium hydride (MgHz) nanoparticles. Thermal decomposition of organomagnesium is a promising method to obtain magnesium nanoparticles in simple step and with high yield. Yet, the resulting decomposition products would depend on the precursors, conditions, and medium during decomposition. Di-n-butylmagnesium is the best precursor investigated in the study. The mediums also determined the physical properties of MgHz from di-n-butylmagnesium; hydrogenolysis in dry solid conditions led to materials capable to store 7.1 wt% hydrogen capacity with fast desorption kinetics at 300 •c. Similar kinetics also being observed in the material obtained from hydrogenolysis of di-n-butylmagnesium in cyclohexane but with only 5.5 wt% capacity due to more hydrocarbon residue from solvent. Other promising method is through catalytical hydrogenation of MgAnthracene.3THF complex which could produce MgH2 nanoparticles in high yield and with good economical value. Despite having kinetic improvements, the thermodynamic limitations are still causing high temperature requirement for hydrogen desorption from these materials. Indeed some theoretical studies showed that significant destabilization can only occur when the nanoparticles sizes are less than 5 nm. The methods were further extended by introducing other compounds such as surfactants and polymers to obtain much smaller size nanoparticles. Herein, the hybrid magnesium polystyrene nanocomposite was successfully synthesised and proven to give protection against oxidations. However, the size did not become smaller with polystyrene but we found the thermodynamic could be altered by the functional groups on the polystyrene. To achieve smaller particle size, polystyrene wtth different nanostructures such as star, dendrimers, and hyperbranched were synthesised and used as templates for limiting the particle growth. Declaration relating to dlspoeltion of project thnlsldlssertatlon I hereby grant to the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or in part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all property rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstracts International (this is applicable to doctoral theses only). ... ... ~ .~ . I. .~. .!..'?:. 9.~ f ... ....... ... ../ -::~ :1 . ~·~Witness· ··~ · · · Date The University recognises that there may be exceptional circumstances requiring restrictions on copying or conditions on use. Requests for restriction for a period of up to 2 years must be made in writing. Requests for a longer period of restriction may be considered in exceptional circumstances and require the approval of the Dean of Graduate Research. FOR OFFICE USE ONLY Date of completion of requirements for Award: THIS SHEET IS TO BE GLUED TO THE INSIDE FRONT COVER OF THE THESIS COPYRK3HTSTATBMENT 'I hereby grant the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or part in the University libraries in al tonns of media, now or here after known, subject to the provisions of the Copyright Ad 1968. I retain al proprietary r1ghts, such as patent rights. I also retain the right to use in Mure works (such as artides or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstract International (this is applicable to doctoral theses only). I have either used no substantial portions of copyright material in my thesis or I have obtained permission to use copyright material; v.tlere permission has not been granted I have applied/WiU apply for a partial restriction of the digital copy of my thesis or dissertation.' Signed ··· ·· ·· ···~··· ·· · ····· · · ········ ··· ·· · ··· · ··· · · ··· ········· 2oc(" Date .......-z.-~.. ... ......I~... .....I ....... ... ............... ........................... AUTHENllCITY STATEMENT 'I oeftlfy that the Ubrary deposit digital COf1f Is a direct equivalent of the final officialy approved version of my thesis. No emendation of content has occurred and if there are any minor variations in formatting, they are the result of the conversion to digital format.' Signed ........~ .. ................ ................................ Date .. ... ..?:. "'::!.. / .. ~ .. !.!:-. .'?.~.f. ... ...... ............................... .. ORIGINALITY STATEMENT 'I hereby dedare that this submission Is my own work and to the best of my knowledge it contains no materials previously published or written by another person, or substantial proportions of material which have been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explldtly acknowledged in the thesis. I also dedare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or In style, presentation and linguistic expression Is acknowledged.' Signed .............. ~ .............................. .. 2.?> I~ I ·?.-o 15' Date Abstract ABSTRACT Nanostructuring metal hydride has been identified as a potential approach to overcome kinetics and thermodynamic limitations due to the large surface area and high surface energy of nanomaterials. However, in practice the synthesis of such nanosized materials with controlled properties is a real challenge. In particular, the high reactivity of magnesium – a promising material for hydrogen storage - challenges its synthesis at the nanoscale. Hence, this thesis aims to explore different strategies based on wet synthesis methods to synthesize and stabilize magnesium hydride (MgH2) nanoparticles. Thermal decomposition of organomagnesium is a promising method to obtain magnesium nanoparticles in simple steps and with high yield. Yet, the resulting decomposition products would depend on the precursors, conditions, and medium during decomposition. Di-n- butylmagnesium is the best precursor investigated in the study. The mediums also determined the physical properties of MgH2 from di-n-butylmagnesium; hydrogenolysis in dry solid conditions which led to materials capable of storing 7.1 wt% hydrogen capacity with fast desorption kinetics at 300 °C. Similar kinetics were also observed in the material obtained from hydrogenolysis of di-n-butylmagnesium in cyclohexane but with only 5.5 wt% capacity due to more hydrocarbon residue from solvent. Another promising method is through catalytical hydrogenation of MgAnthracene.3THF complex which could produce MgH2 nanoparticles in high yield and with good economical value. Despite having kinetic improvements, the thermodynamic limitations still cause a high temperature requirement for hydrogen desorption from these materials. Indeed some theoretical studies showed that significant destabilization can only occur when the nanoparticles sizes are less than 5 nm. The methods were further extended by introducing v Abstract other compounds such as surfactants and polymers to obtain much smaller sized nanoparticles. Herein, the hybrid magnesium polystyrene nanocomposite was successfully synthesised and proven to give protection against oxidation. However, the size did not become smaller with polystyrene but we found the thermodynamic could be altered by functional groups on the polystyrene. To achieve smaller particle size, polystyrene with different nanostructures such as star, dendrimers, and hyperbranched were synthesised and used as templates for limiting the particle growth. vi Acknowledgements ACKNOWLEDGEMENTS First and foremost, praises and thanks to the God, the Almighty, for His showers of blessings throughout my research work to complete the research successfully. Looking back, five years ago when I just finished my undergraduate school, I never thought that I would end up doing a PhD or stayed in the same university for almost another
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