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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Sputtered magnesium aluminum and magnesium aluminum titanium alloys for hydrogen storage

Haagsma, Julian Unknown Date
No description available.
2

Towards Hydrogen Storing Systems for Vehicular Applications

Little, Vanessa Renee 24 December 2013 (has links)
The rising environmental and financial consequences of using fossil fuels as an energy source and energy carrier are a global concern. Described herein are two hydrogen-storing technologies, each of which was envisioned as a potential solution to said consequences: hydrogen-storing polymethylpyridylsiloxanes for use as an alternative energy carrier to fossil fuels; and thermally regenerative fuel cell systems to supplement or supplant vehicular alternators. A thermally regenerative fuel cell (TRFC) system is being developed to convert waste heat from an internal combustion engine (ICE) system into electricity that can be used to power auxiliary vehicular components. The TRFC system will comprise a dehydrogenation reactor and a fuel cell positioned relative to the ICE system such that the two components are held at 200 °C and 100 °C, respectively. 1-Phenyl-1-propanol has been identified as an optimal hydrogen storing liquid (XH2) that will selectively dehydrogenate over a heterogeneous catalyst to give a dehydrogenated liquid (propiophenone, X) and H2. The heterogeneous catalyst that currently provides the best selectivity (99.65%) for X at 200 °C is Pd/SiO2. A selectivity of ≥ 99.9% was desired to obtain the longest possible operational lifetime for the working fluids XH2/X. To increase the selectivity for X from 99.65% to ≥ 99.9%, size and shape specific Pd nanoparticles were synthesized. Pd nanocubes (20 nm) provided the best selectivity for X at 99.26%. It was concluded that a reproducible selectivity for X of ≥ 99.9% was not currently obtainable, and that a selectivity for X no greater than 99 % should be assumed when calculating the working fluids’ operational lifetime. Hydrogen-storing polymethylpyridylsiloxanes were proposed as energy carrier alternatives to fossil fuels. Polymethylpyridylsiloxanes were considered, in part, due to the expansive liquid ranges of siloxane polymers [-40 ˚C to 250 ˚C]; this would allow the polymethylpyridylsiloxanes to be stored and pumped into vehicles using existing refueling infrastructure. Polymethylpyridylsiloxanes, and analogs thereof, however, were not successfully synthesized and reversibly hydrogenated: either the desired product(s) could not be synthesized, isolated, and/or purified; or, hydrogenation resulted in product decomposition. It was concluded, therefore, that implementing polymethylpyridylsiloxanes as hydrogen-storing liquids is not viable. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-12-24 01:01:16.857
3

Electrochemical energy conversion using metal hydrides hydrogen storage materials

Jonas, Ncumisa Prudence January 2010 (has links)
<p>Metal hydrides hydrogen storage materials have the ability to reversibly absorb and release large amounts of hydrogen at low temperature and pressure. In this study, metal hydride materialsemployed as negative electrodes in Ni-MH batteries are investigated. Attention is on AB5 alloys due to their intermediate thermodynamic properties. However, AB5 alloys a have&nbsp / tendency of forming oxide film on their surface which inhibits hydrogen dissociation and penetration into interstitial sites leading to reduced capacity. To redeem this, the materials were micro-encapsulated by electroless deposition with immersion in Pd and Pt baths. PGMs were found to increase activation, electrochemical activity and H2 sorption kinetics of the MH alloys. Between the two catalysts the one which displayed better performance was chosen. The materials were characterized by X-ray difractommetry, and the alloys presented hexagonal CaCu5 &ndash / type&nbsp / structure of symmetry P6/mmm. No extra phases were found, all the modified electrodes displayed the same behavior as the parent material. No shift or change in peaks which corresponded to Pd or Pt were observed. Scanning Electron Microscopy showed surface morphology of the materials modified with Pd and Pt particles, the effect of using different reducing agents (i.e., N2H4 and NaH2PO2), and alloys functionalized with &gamma / -aminosopropyltrietheosilane solution prior to Pd deposition. From all the surface modified alloys, Pt and Pd particles were observed on the&nbsp / surface of the AB5 alloys. Surface modification without pre-functionalization had non-uniform coatings, but the prefunctionalized exhibited more uniform coatings. Energy dispersive X-ray Spectroscopy and Atomic Absorption Spectroscopy determined loading of the Pt and Pd on the surface of all the alloys, and the results were as follows: EDS ( Pt 13.41 and Pd 31.08wt%), AAS (Pt 0.11 and Pd 0.78wt%). Checking effect of using different reducing agents N2H4 and NaH2PO2 for electroless Pd plating the results were as follows: EDS (AB5_N2H4_Pd- 7.57 and AB5_NaH2PO2_Pd- 31.08wt%), AAS (AB5_N2H4_Pd- 11.27 and AB5_NaH2PO2_Pd- 0.78wt%). For the AB5 alloys pre-functionalized with &gamma / -APTES, the results were: EDS (10.24wt%) and AAS (0.34wt%). Electrochemical characterization was carried out by charge/discharge cycling controlled via potential to test the AB5 alloy. Overpotential for unmodified, Pt and Pd modified&nbsp / electrodes were -1.1V, -1.24V, and -1.60V, respectively. Both modified electrodes showed discharge overpotentials at lower values implying higher specific power for the battery in comparison with the unmodified electrodes. However, Pd electrode exhibited higher specific power than Pt. To check the effect of the reducing agent the results were as follows: AB5_ N2H4_Pd (0.4V) and AB5_NaH2PO2_Pd (-0.2V), sodium hypophosphite based alloy showing lower overpotential values, implying it had higher specific power than hydrazine based bath. Alloy prefunctionalized with &gamma / -APTES, the overpotential was (0.28V), which was higher than -0.2V of the alloy without pre-functionalization, which means pre-functionalization with &gamma / -APTES did not improve the performance of the alloy electrode. Polarization resistance of the electrodes was investigated with Electrochemical Impedance Spectroscopy. The unmodified alloy showed high resistance of&nbsp / 21.6884 while, both Pt and Pd modified electrodes exhibited decrease 14.7397 and 12.1061 respectively, showing increase in charge transfer for the modified electrodes. Investigating the effect of the reducing agent, the alloys exhibited the following results: (N2H4 97.8619 and NaH2PO2 12.1061) based bath. Alloy pre-functionalized with &gamma / -APTES displayed the&nbsp / resistance of 9.3128. Cyclic Voltammetry was also used to study the electrochemical activity of the alloy electrodes. The voltammograms obtained displayed the anodic current peak at -0.64V&nbsp / o -0.65V for the Pt and Pd modified electrodes, respectively. Furthermore, the electrode which was not coated with Pt or Pd the current peak occurred at -0.59V. The Pd and Pt coated&nbsp / alloy electrodes represented lower discharge overpotentials, which are important to improve the battery performance. Similar results were also observed with alloy electrodes Pd modified&nbsp / using N2H4 (-0.64V) and NaH2PO2 (-0.65V). For the electrode modified with and without &gamma / -APTES the over potentials were the same (-0.65V). PGM deposition has shown to significantly&nbsp / improve activation and hydrogen sorption performance and increased the electro-catalytic activity of these alloy electrodes. Modified electrodes gave better performance than the unmodified&nbsp / electrodes. As a result, Pd was chosen as the better catalyst for the modification of AB5 alloy. Based on the results, it was concluded that Pd electroless plated using NaH2PO2 reducing agent&nbsp / had better performance than electroless plating using N2H4 as the reducing agent. Alloy electrode pre-functionalized with &gamma / -APTES gave inconsistent results, and this phenomenon needs to&nbsp / be further investigated. In conclusion, the alloy modified with Pd employing NaH2PO2 based electroless plating bath exhibited consistent results, and was found to be suitable candidate for&nbsp / use in Ni-MH batteries.</p>
4

Hybrid density functional studies of hydrogen storage related molecular systems /

Diaconu, Cristian V. January 2005 (has links)
Thesis (Ph.D.)--Brown University, 2005. / Vita. Thesis advisor: Jimmie D. Doll. Includes bibliographical references (leaves 159-170). Also available online.
5

Electrochemical energy conversion using metal hydrides hydrogen storage materials

Jonas, Ncumisa Prudence January 2010 (has links)
<p>Metal hydrides hydrogen storage materials have the ability to reversibly absorb and release large amounts of hydrogen at low temperature and pressure. In this study, metal hydride materialsemployed as negative electrodes in Ni-MH batteries are investigated. Attention is on AB5 alloys due to their intermediate thermodynamic properties. However, AB5 alloys a have&nbsp / tendency of forming oxide film on their surface which inhibits hydrogen dissociation and penetration into interstitial sites leading to reduced capacity. To redeem this, the materials were micro-encapsulated by electroless deposition with immersion in Pd and Pt baths. PGMs were found to increase activation, electrochemical activity and H2 sorption kinetics of the MH alloys. Between the two catalysts the one which displayed better performance was chosen. The materials were characterized by X-ray difractommetry, and the alloys presented hexagonal CaCu5 &ndash / type&nbsp / structure of symmetry P6/mmm. No extra phases were found, all the modified electrodes displayed the same behavior as the parent material. No shift or change in peaks which corresponded to Pd or Pt were observed. Scanning Electron Microscopy showed surface morphology of the materials modified with Pd and Pt particles, the effect of using different reducing agents (i.e., N2H4 and NaH2PO2), and alloys functionalized with &gamma / -aminosopropyltrietheosilane solution prior to Pd deposition. From all the surface modified alloys, Pt and Pd particles were observed on the&nbsp / surface of the AB5 alloys. Surface modification without pre-functionalization had non-uniform coatings, but the prefunctionalized exhibited more uniform coatings. Energy dispersive X-ray Spectroscopy and Atomic Absorption Spectroscopy determined loading of the Pt and Pd on the surface of all the alloys, and the results were as follows: EDS ( Pt 13.41 and Pd 31.08wt%), AAS (Pt 0.11 and Pd 0.78wt%). Checking effect of using different reducing agents N2H4 and NaH2PO2 for electroless Pd plating the results were as follows: EDS (AB5_N2H4_Pd- 7.57 and AB5_NaH2PO2_Pd- 31.08wt%), AAS (AB5_N2H4_Pd- 11.27 and AB5_NaH2PO2_Pd- 0.78wt%). For the AB5 alloys pre-functionalized with &gamma / -APTES, the results were: EDS (10.24wt%) and AAS (0.34wt%). Electrochemical characterization was carried out by charge/discharge cycling controlled via potential to test the AB5 alloy. Overpotential for unmodified, Pt and Pd modified&nbsp / electrodes were -1.1V, -1.24V, and -1.60V, respectively. Both modified electrodes showed discharge overpotentials at lower values implying higher specific power for the battery in comparison with the unmodified electrodes. However, Pd electrode exhibited higher specific power than Pt. To check the effect of the reducing agent the results were as follows: AB5_ N2H4_Pd (0.4V) and AB5_NaH2PO2_Pd (-0.2V), sodium hypophosphite based alloy showing lower overpotential values, implying it had higher specific power than hydrazine based bath. Alloy prefunctionalized with &gamma / -APTES, the overpotential was (0.28V), which was higher than -0.2V of the alloy without pre-functionalization, which means pre-functionalization with &gamma / -APTES did not improve the performance of the alloy electrode. Polarization resistance of the electrodes was investigated with Electrochemical Impedance Spectroscopy. The unmodified alloy showed high resistance of&nbsp / 21.6884 while, both Pt and Pd modified electrodes exhibited decrease 14.7397 and 12.1061 respectively, showing increase in charge transfer for the modified electrodes. Investigating the effect of the reducing agent, the alloys exhibited the following results: (N2H4 97.8619 and NaH2PO2 12.1061) based bath. Alloy pre-functionalized with &gamma / -APTES displayed the&nbsp / resistance of 9.3128. Cyclic Voltammetry was also used to study the electrochemical activity of the alloy electrodes. The voltammograms obtained displayed the anodic current peak at -0.64V&nbsp / o -0.65V for the Pt and Pd modified electrodes, respectively. Furthermore, the electrode which was not coated with Pt or Pd the current peak occurred at -0.59V. The Pd and Pt coated&nbsp / alloy electrodes represented lower discharge overpotentials, which are important to improve the battery performance. Similar results were also observed with alloy electrodes Pd modified&nbsp / using N2H4 (-0.64V) and NaH2PO2 (-0.65V). For the electrode modified with and without &gamma / -APTES the over potentials were the same (-0.65V). PGM deposition has shown to significantly&nbsp / improve activation and hydrogen sorption performance and increased the electro-catalytic activity of these alloy electrodes. Modified electrodes gave better performance than the unmodified&nbsp / electrodes. As a result, Pd was chosen as the better catalyst for the modification of AB5 alloy. Based on the results, it was concluded that Pd electroless plated using NaH2PO2 reducing agent&nbsp / had better performance than electroless plating using N2H4 as the reducing agent. Alloy electrode pre-functionalized with &gamma / -APTES gave inconsistent results, and this phenomenon needs to&nbsp / be further investigated. In conclusion, the alloy modified with Pd employing NaH2PO2 based electroless plating bath exhibited consistent results, and was found to be suitable candidate for&nbsp / use in Ni-MH batteries.</p>
6

Electrochemical energy conversion using metal hydrides hydrogen storage materials

Jonas, Ncumisa Prudence January 2010 (has links)
Magister Scientiae - MSc / Metal hydrides hydrogen storage materials have the ability to reversibly absorb and release large amounts of hydrogen at low temperature and pressure. In this study, metal hydride materials employed as negative electrodes in Ni-MH batteries are investigated. Attention is on AB5 alloys due to their intermediate thermodynamic properties. However, AB5 alloys a have tendency of forming oxide film on their surface which inhibits hydrogendissociation and penetration into interstitial sites leading to reduced capacity. To redeem this, the materials were micro-encapsulated by electroless deposition with immersion in Pd and Pt baths. PGMs were found to increase activation, electrochemical activity and H2 sorption kinetics of the MH alloys. Between the two catalysts the one which displayed better performance was chosen. The materials were characterized by X-ray difractommetry, and the alloys presented hexagonal CaCu 5–type structure of symmetry P6/mmm. No extra phases were found, all the modified electrodes displayed the same behavior as the parent material. No shift or change in peaks which corresponded to Pd or Pt were observed. Scanning Electron Microscopy showed surface morphology of the materials modified with Pd and Pt particles, the effect of using different reducing agents (i.e ., N2H4 and NaH2PO2), and alloys functionalized with γ-aminosopropyltrietheosilane solution prior to Pd deposition. From all the surface modified alloys, Pt and Pd particles were observed on the surface of the AB5 alloys. Surface modification without pre-functionalization had non-uniform coatings, but the pre- functionalized exhibited more uniform coatings. Energy dispersive X-ray Spectroscopy and Atomic Absorption Spectroscopy determined loading of the Pt and Pd on the surface of all the alloys, and the results were as follows: EDS ( Pt 13.41and Pd 31.08wt%), AAS (Pt 0.11 and Pd 0.78wt%). Checking effect of using different reducing agents N2H4 and NaH2PO2 for electroless Pd plating the results were as follows: EDS (AB5_N2H4_Pd- 7.57 and AB 5_NaH2PO2_Pd- 31.08wt%), AAS (AB5_N2H4_Pd- 11.27 and AB5_NaH2PO2_Pd- 0.78wt%). For the AB5 alloyspre-unctionalized with γ-APTES, the results were: EDS (10.24wt%) and AAS (0.34wt%). Electrochemical characterization was carried out by charge/discharge cycling controlled via potential to test the AB5 alloy. Overpotential for unmodified, Pt and Pd modified electrodes were-1.1V, -1.24V, and -1.60V, respectively. Both modified electrodes showed discharge overpotentials at lower values implying higher specific power for the battery in comparison with the unmodified electrodes. However, Pd electrode exhibited higher specific power than Pt. To check the effect of the reducing agent the results were as follows: AB5_ N2H4_Pd (0.4V) and AB5_NaH2PO2_Pd (-0.2V), sodium hypophosphite based alloy showing lower overpotential values, implying it had higher specific power than hydrazine based bath. Alloy pre-functionalized with γ-APTES, the overpotential was (0.28V), which was higher than -0.2V of the alloy without pre-functionalization, which means pre-functionalization with γ-APTES did not improve the performance of the alloy electrode. Polarization resistance of the electrodes was investigated with Electrochemical Impedance Spectroscopy. The unmodified alloy showed high resistance of 21.6884 while, both Pt and Pd modified electrodes exhibited decrease 14.7397 and 12.1061 respectively, showing increase in charge transfer for the modified electrodes. Investigating the effect of the reducing agent, the alloys exhibited the following results: (N2H497.8619 and NaH2PO212.1061 ) based bath. Alloy pre-functionalized with γ-APTES displayed the resistance of 9.3128. Cyclic Voltammetry was also used to study the electrochemical activity of the alloy electrodes. The voltammograms obtained displayed the anodic current peak at -0.64V to -0.65V for the Pt and Pd modified electrodes, respectively. Furthermore, the electrode which was not coated with Pt or Pd the current peak occurred at -0.59V. The Pd and Pt coated alloy electrodes represented lower discharge overpotentials, which are important to improve the battery performance. Similar results were also observed with alloy electrodes Pd modified using N2H4(-0.64V) and NaH2PO2(-0.65V). For the electrode modified with and without γ-APTES the over potentials were thesame (-0.65V). PGM deposition has shown to significantly improve activation and hydrogen sorption performance and increased the electro-catalytic activity of these alloy electrodes. Modified electrodes gave better performance than the unmodified electrodes. As a result, Pd was chosen as the better catalyst for the modification of AB5 alloy. Based on the results, it was concluded that Pd electroless plated using NaH2PO2 reducing agent had better performance than electroless plating using N2H4 as the reducing agent. Alloy electrode pre-functionalized with γ-APTES gave inconsistent results, and this phenomenon needs to be further investigated. In conclusion, the alloy modified with Pd employing NaH 2PO2 usased electroless plating bath exhibited consistent results, and was found to be suitable candidate for use in Ni-MH batteries / South Africa
7

Towards a standard methodology for determining hydrogen storage in nanoporous materials

Hruzewicz-Kolodziejczyk, Anna January 2013 (has links)
Hydrogen has a great potential to become a wide-scale, carbon free, sustainable energy carrier of the future. However its implementation and final utilization especially in mobile applications is still limited because of several technological and socio-economical barriers, mainly to do with safe, efficient storage of hydrogen with high gravimetric and volumetric storage capacities. Physisorption into nanoporous materials is an attractive option as it benefits from rapid, fully reversible adsorption/desorption and can store significant amounts of hydrogen at more moderate temperature and pressures conditions than conventional liquefaction (20.3 K) or compression (350‒700 bar). Nevertheless, the critical challenge exists to define the experimental methods that allow accurate hydrogen sorption determination and reduce discrepancies in measurements between different laboratories. This thesis presents an investigation of the experimental methodology of hydrogen sorption in porous materials. A set of nanoporous samples and characterisation techniques have been tested rigorously to explore experimental uncertainty and provide universally reproducible procedures. The validity of the standard methods and some new approaches for experimental data collection and analysis are presented. High repeatability of gas sorption isotherms measured gravimetrically and volumetrically at 77 K on reference TE 7 III carbon beads sample has been demonstrated in-house. A study has been conducted between seven laboratories to evaluate the reproducibility of nitrogen/hydrogen isotherms at 77 K according to a defined test protocol. Statistical analysis yields very good agreement between nitrogen and hydrogen sorption results. The Brunauer-Emmett-Teller surface area of 777.8 ± 6.2 m2 g-1 and Dubinin-Radushkevich micropore volume of 0.3766 ± 0.0078 cm3 g-1, have been determined. The excess hydrogen sorption capacities are found to be 1.65 ± 0.04 wt% and 2.33 ± 0.007 wt% for 1 bar and 20 bar hydrogen pressure, respectively. This study concludes that the accuracy of hydrogen sorption measurements have been pushed forward and methodology proposed here could contribute to improvements in certification of future hydrogen sorption methods.
8

First Principle Studies of Functional Materials : Spintronics, Hydrogen Storage and Cutting Tools

Silvearv, Fredrik January 2011 (has links)
The properties of functional materials have been studied with density functional theory. The first type of materials that have been investigated is the so called diluted magnetic semiconductors. It is a new class of materials that could offer enhanced functionality by making use of spin in addition to the charge of the electron. (Mn,Al) co-doped ZnO has been investigated regarding the Al significance on ferromagnetic behavior using density functional theory within the generalized-gradient approximation plus on-site Coulomb interaction. Despite the presence of Al the system always shows antiferromagnetic behavior. The role of intrinsic defects on ferromagnetism in pure and Cr doped In2O3 was also studied. For pristine In2O3, In vacancy and O interstitial states are completely spin polarized. Moreover, these hole states will create Cr ions in mixed valence state, giving rise to a strong ferromagnetic coupling. The second type of functional materials studied are hydrogen storage materials for mobile applications. These materials are considered as alternative if hydrogen is to replace fossil fuels as a energy carrier. In the view of this a series of compounds containing boron, nitrogen and hydrogen has been examined with respect to electronic structure, dehydrogenation energy and hydrogen diffusion properties. One compound, NH3BH3, has many desirable properties as a hydrogen storage material. In an effort to improve those properties, one of the H atoms in the NH3 group was replaced by Li, Na or Sr. The calculated hydrogen removal energies of the hydrogen release reactions were found to be significantly improved. Finally, a coating material, Al2O3, for wear resistant coatings on high performance cemented carbide cutting tools has been investigated. Chemical vapor deposition grown Al2O3 has been used for decades by the industry. To improve the growth process H2S is added to the gas mixture. The catalytic effect of H2S on the AlCl3/H2/CO2/HCl chemical vapor deposition process has been investigated on an atomistic scale. By applying a combined approach of thermodynamic modeling and density functional theory it seems that H2S acts as mediator for the oxygenation of the Al-surface which will in turn increase the growth rate of Al2O3.
9

Lightweight Intermetallics with Laves Structures as Potential Hydrogen Storage Materials

Billet, Beau 22 May 2013 (has links)
No description available.
10

Nanostructured complex hydride systems for solid state hydrogen storage

Jang, Minchul 07 December 2011 (has links)
The present work reports a study of the effects of the formation of a nanostructure induced by high-energy ball milling, compositions, and various catalytic additives on the hydrogen storage properties of LiNH2-LiH and LiNH2-MgH2 systems. The mixtures are systematically investigated using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and a Sieverts-type apparatus. The results indicate that microstructural refinement (particle and grain size) induced by ball milling affects the hydrogen storage properties of LiNH2-LiH and LiNH2-MgH2 systems. Moreover, the molar ratios of the starting constituents can also affect the dehydrogenation/hydrogenation properties. In the LiNH2-LiH system, high-energy ball milling is applied to the mixtures of LiNH2 and LiH with molar ratios of 1:1, 1:1.2 and 1:1.4 LiH. The lowest apparent activation energy is observed for the mixture of LiNH2-LiH (1:1.2) milled for 25 h. The major impediment in the LiNH2-LiH system is the hydrolysis and oxidation of LiH, which causes a fraction of LiH to be inactive in the intermediate reaction of NH3+LiH→LiNH2+H2. Therefore, the LiNH2-LiH system always releases NH3, as long as a part of LiH becomes inactive, due to hydrolysis/oxidation, and does not take part in the intermediate reaction. To prevent LiH from undergoing hydrolysis/oxidation during desorption/absorption, 5 wt. % graphite is incorporated in the (LiNH2+1.2LiH) system. The DSC curve of the mixture does not show a melting peak of retained LiNH2, indicating that graphite can prevent or at least substantially reduce the oxidation/hydrolysis of LiH. Moreover, compared to the mixture without graphite, the mixture with graphite shows more hydrogen capacity, thus this mixture desorbs ~5 wt.% H2, which is close to the theoretical capacity. This system is fully reversible in the following reaction: LiNH2+LiH→Li2NH+H2. However, the equilibrium temperature at the atmospheric pressure of hydrogen (0.1 MPa H2) is 256.8°C for (LiNH2+1.2LiH) mixture, which is too high for use in onboard applications. To overcome the thermodynamic barrier associated with the LiNH2/LiH system, LiH is substituted by MgH2; therefore, the (LiNH2+nMgH2) (n=0.55, 0.6 and 0.7) system is investigated first. These mixtures are partially converted to Mg(NH2)2 and LiH by the metathesis reaction upon ball milling. In this system, hydrogen is desorbed in a two-step reaction: [0.5xMg(NH2)2+xLiH]+[(1-x)LiNH2+(0.5-0.5x)MgH2]→0.5Li2Mg(NH)2+1.0H2 and 0.5Li2Mg(NH)2+MgH2→0.5Mg3N2+LiH+H2. Moreover, this system is fully reversible in the following reaction: Li2Mg(NH)2+2H2→ Mg(NH2)2+2LiH. Step-wise desorption tests show that the enthalpy and entropy change of the first reaction is -46.7 kJ/molH2 and 136.1 J/(molK), respectively. The equilibrium temperature at 0.1 bar H2 is 70.1°C, which indicates that this system has excellent potential for onboard applications. The lowest apparent activation energy of 71.7 kJ/mol is observed for the molar ratio of 1:0.7MgH2 milled for 25 h. This energy further decreases to 65.0 kJ/mol when 5 wt.% of n-Ni is incorporated in the system. Furthermore, the molar ratio of MgH2/LiNH2 is increased to 1.0 and 1.5 to increase the limited hydrogen storage capacity of the (LiNH2+0.7MgH2) mixture. It has been reported that the composition changes can enhance the hydrogen storage capacity by changing the dehydrogenation/hydrogenation reaction pathways. However, theoretically predicted LiMgN is not observed, even after dehydrogenation at 400°C. Instead of this phase, Li2Mg(NH)2 and Mg3N2 are obtained by dehydrogenation at low and high temperatures, respectively, regardless of the milling mode and the molar ratio of MgH2/LiNH2. The only finding is that the molar ratio of MgH2/LiNH2 can significantly affect mechano-chemical reactions during ball milling, which results in different reaction pathways of hydrogen desorption in subsequent heating processes; however, the reaction’s product is the same regardless of the milling mode, the milling duration and their composition. Therefore, the (LiNH2+0.7MgH2) mixture has the greatest potential for onboard applications among Li-Mg-N-H systems due to its high reversible capacity and good kinetic properties.

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