... are a few scattered studies of NaNH 2 -containing systems such as NaNH 2 −NaBH 4 ,(12, 17 ...... more ... are a few scattered studies of NaNH 2 -containing systems such as NaNH 2 −NaBH 4 ,(12, 17 ... Mg(NH 2 ) 2 and NaMgH 3 as intermediary phases with the overall decomposition reaction being ... in a 1:1 ratio, the system was shown to undergo a dehydrogenation process according ...
The thermodynamic properties of magnesium hydride nanoparticles have been investigated by hydroge... more The thermodynamic properties of magnesium hydride nanoparticles have been investigated by hydrogen decomposition pressure measurements using the Sieverts technique. A mechanochemical method was used to synthesize MgH(2) nanoparticles (down to approximately 7 nm in size) embedded in a LiCl salt matrix. In comparison to bulk MgH(2), the mechanochemically produced MgH(2) with the smallest particle size showed a small but measurable decrease in the decomposition reaction enthalpy (DeltaH decrease of 2.84 kJ/mol H(2) from DeltaH(bulk) = 74.06 +/- 0.42 kJ/mol H(2) to DeltaH(nano) = 71.22 +/- 0.49 kJ/mol H(2)). The reduction in DeltaH matches theoretical predictions and was also coupled with a similar reduction in reaction entropy (DeltaS decrease of 3.8 J/mol H(2)/K from DeltaS(bulk) = 133.4 +/- 0.7 J/mol H(2)/K to DeltaS(nano) = 129.6 +/- 0.8 J/mol H(2)/K). The thermodynamic changes in the MgH(2) nanoparticle system correspond to a drop in the 1 bar hydrogen equilibrium temperature (T(1 bar)) by approximately 6 degrees C to 276.2 +/- 2.4 degrees C in contrast to the bulk MgH(2) system at 281.8 +/- 2.2 degrees C. The reduction in the desorption temperature is less than that expected from theoretical studies due to the decrease in DeltaS that acts to partially counteract the effect from the change in DeltaH.
Concerns over green house gas emissions and their climate change effects have lead to a concerted... more Concerns over green house gas emissions and their climate change effects have lead to a concerted effort into environmental friendly technologies. One such emphasis has been on the implementation of the hydrogen economy. There are four major impediments to the implementation of a hydrogen economy: hydrogen production, distribution, storage and conversion. This thesis is focused on exploring the hydrogen storage problem. Hydrogen can be stored by a wide range of methods. One of these methods involves using a secondary material that stores hydrogen by either physisorbing hydrogen onto its surfaces or by reacting with it to form a new compound. Of the wide variety of materials that can interact with hydrogen, three different materials were chosen; (1) nano-structured materials of high surface area; mesoporous silica (MCM-41) and titanate nanotubes, and (2) hydrides of Ti-Mg-Ni alloys. Results of the hydrogen on mesoporous silica (MCM-41) showed 1 wt.% H[subscript]2 to a maximum of 2 wt...
One of the limitations to the widespread use of hydrogen as an energy carrier is its storage in a... more One of the limitations to the widespread use of hydrogen as an energy carrier is its storage in a safe and compact form. Herein, recent developments in effective high-capacity hydrogen storage materials are reviewed, with a special emphasis on light compounds, including those based on organic porous structures, boron, nitrogen, and aluminum. These elements and their related compounds hold the promise of high, reversible, and practical hydrogen storage capacity for mobile applications, including vehicles and portable power equipment, but also for the large scale and distributed storage of energy for stationary applications. Current understanding of the fundamental principles that govern the interaction of hydrogen with these light compounds is summarized, as well as basic strategies to meet practical targets of hydrogen uptake and release. The limitation of these strategies and current understanding is also discussed and new directions proposed.
ABSTRACT A simplified techno-economic model has been used as a screening tool to explore the fact... more ABSTRACT A simplified techno-economic model has been used as a screening tool to explore the factors that have the largest impact on the costs of using metal hydrides for concentrating solar thermal storage. The installed costs of a number of paired metal hydride concentrating solar thermal storage systems were assessed. These comprised of magnesium-based (MgH2, Mg2FeH6, NaMgH3, NaMgH2F) high-temperature metal hydrides (HTMH) for solar thermal storage and Ti1.2Mn1.8H3.0 as the low-temperature metal hydride (LTMH) for hydrogen storage. A factored method approach was used for a 200 MWel power plant operating at a plant capacity factor (PCF) of 50% with 7 hours of thermal storage capacity at full-load. In addition, the hydrogen desorption properties of NaMgH2F have been measured for the first time. It has a practical hydrogen capacity of 2.5 wt% (2.95 wt% theoretical) and desorbs hydrogen in a single-step process above 478 oC and in a two-step process below 478 oC. In both cases the final decomposition products are NaMgF3, Na and Mg. Only the single-step desorption is suitable for concentrating solar thermal storage applications and has an enthalpy of 96.8 kJ mol-1 H2 at the midpoint of the hydrogen desorption plateau. The techno-economic model showed that the cost of the LTMH, Ti1.2Mn1.8H3.0, is the most significant component of the system and that its cost can be reduced by increasing the operating temperature and enthalpy of hydrogen absorption in the HTMH that, in turn, reduces the quantity of hydrogen required in the system for an equivalent electrical output. The result is that, despite the fact that the theoretical thermal storage capacity of NaMgH2F (1416 kJ kg-1) is substantially lower than the theoretical values for MgH2 (2814 kJ kg-1), Mg2FeH6 (2090 kJ kg-1) and NaMgH3 (1721 kJ kg-1), its higher enthalpy and operating temperature leads to the lowest installed cost of the systems considered. A further decrease in cost could be achieved by utilizing metal hydrides with yet higher enthalpies and operating temperatures or by finding a lower cost option for the LTMH.
ABSTRACT The addition of Group IV elements of Si, Ge or Sn to Mg-based hydrides has led to the su... more ABSTRACT The addition of Group IV elements of Si, Ge or Sn to Mg-based hydrides has led to the successful destabilisation of MgH2 or NaMgH3, resulting in hydrogen release at lower temperatures. This is the first time a direct comparison has been made with all the samples prepared and characterised using identical conditions. Pure MgH2 desorbs hydrogen at a pressure of 1 bar at 282 °C, a temperature too high for typical mobile applications. The addition of Group IV metals to MgH2 causes the formation of intermetallic compounds (Mg2Si, Mg2Ge and Mg2Sn) upon hydrogen release. Theoretical calculations show promising thermodynamic equilibrium conditions for these systems. Experimentally, these conditions were difficult to achieve, however, hydrogen desorption results show that Ge has the most significant effect in allowing low temperature hydrogen release, followed by Sn, then Si. It was found that Si also has a beneficial effect on NaMgH3, reducing the desorption temperature.
ABSTRACT Aluminium sulphide (Al2S3) is predicted to effectively destabilise sodium aluminium hydr... more ABSTRACT Aluminium sulphide (Al2S3) is predicted to effectively destabilise sodium aluminium hydride (NaAlH4) in a single-step endothermic hydrogen release reaction. The experimental results show unexpectedly complex desorption processes and a range of new sulphur containing hydrogen storage materials have been observed. The NaAlH4–Al2S3 system releases a total of 4.9 wt% of H2 that begins below 100 oC without the need for a catalyst. Characterisation via temperature programmed desorption, in situ synchrotron powder X-ray diffraction, ex situ x-ray diffraction, ex situ Fourier transform infrared spectroscopy and hydrogen sorption measurements reveal complex decomposition processes that involve multiple new sulphur-containing hydride compounds. The system shows partial H2 reversibility, without the need for a catalyst, with a stable H2 capacity of ~1.6 wt% over 15 cycles in the temperature range of 200 oC to 300 oC. This absorption capacity is limited by the need for high H2 pressures (>280 bar) to drive the absorption process at the high temperatures required for reasonable absorption kinetics. The large number of new phases discovered in this system suggests that destabilisation of complex hydrides with metal sulphides is a novel but unexplored research avenue for hydrogen storage materials.
ABSTRACT An ordered mesoporous carbon scaffold (CMK-1) has been synthesized and infiltrated with ... more ABSTRACT An ordered mesoporous carbon scaffold (CMK-1) has been synthesized and infiltrated with NaAlH4 nanoparticles by solvent- and melt-infiltration techniques. Small angle X-ray scattering (SAXS), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission Electron Microscopy (TEM) and energy dispersive spectroscopy (EDS) are used to characterize the structure, composition and morphology before and after thermal treatment. This study illuminates some of the problems that can be associated with nanoconfinement of hydrogen storage materials including scaffold contamination, residual solvent contamination, sample morphology changes after heating, and other factors that can be detrimental to the application of these systems. Of particular interest is the expulsion of NaAlH4 decomposition products from the scaffold after heating beyond its melting point under vacuum. This results in the surface of mesoporous carbon particles having arrays of multi-micron-long Al filaments that are >100 nm in diameter. Copyright
Physical chemistry chemical physics : PCCP, Jan 14, 2013
The thermal decomposition of anhydrous Pa3[combining macron] Li2B12H12 was studied in situ by hig... more The thermal decomposition of anhydrous Pa3[combining macron] Li2B12H12 was studied in situ by high resolution synchrotron X-ray diffraction. A first-order phase transition can be observed at 355 °C where the unit cell volume expands by ca. 8.7%. The expanded β-Li2B12H12 polymorph simultaneously decomposes to a hydrogen poor γ-Li2B12H12-x phase. Expansion of the unit cell across the discontinuity is consistent with reorientational motion of B12H12(2-) anions, and the presence of a frustrated Li(+) lattice indicating Li ion conduction.
Dalton transactions (Cambridge, England : 2003), Jan 21, 2014
Rare earth metal borohydrides have been proposed as materials for solid-state hydrogen storage be... more Rare earth metal borohydrides have been proposed as materials for solid-state hydrogen storage because of their reasonably low temperature of decomposition. New synthesis methods, which provide halide-free yttrium and gadolinium borohydride, are presented using dimethyl sulfide and new solvates as intermediates. The solvates M(BH4)3S(CH3)2 (M = Y or Gd) are transformed to α-Y(BH4)3 or Gd(BH4)3 at ~140 °C as verified by thermal analysis. The monoclinic structure of Y(BH4)3S(CH3)2, space group P2₁/c, a = 5.52621(8), b = 22.3255(3), c = 8.0626(1) Å and β = 100.408(1)°, is solved from synchrotron radiation powder X-ray diffraction data and consists of buckled layers of slightly distorted octahedrons of yttrium atoms coordinated to five borohydride groups and one dimethyl sulfide group. Significant hydrogen loss is observed from Y(BH4)3 below 300 °C and rehydrogenation at 300 °C and p(H2) = 1550 bar does not result in the reformation of Y(BH4)3, but instead yields YH3. Moreover, composit...
ABSTRACT We have studied the complex decomposition mechanism of cubic γ-Mg(BH4)2 (Ia3̅d, a = 15.7... more ABSTRACT We have studied the complex decomposition mechanism of cubic γ-Mg(BH4)2 (Ia3̅d, a = 15.7858(1) Å) by in-situ synchrotron X-ray diffraction, temperature-programmed desorption, visual observation of the melt, and Fourier transform infrared (FTIR) spectroscopy. The decomposition and release of hydrogen proceeds through eight distinct steps, including two polymorphic transitions before melting, with a new ε-Mg(BH4)2 phase at ca. 150 °C. After melting, strong changes in sample color from yellow to brown to gray are consistent with the unknown Mg–B–H phase(s) (that diffract with high d-spacing halos) in the sample changing from an average composition of MgB2H5.3 at 325 °C, to MgB2.9H3.2 at 350 °C, and to MgB4.0H3.7 by 450 °C. From 350 to 450 °C, the crystalline Mg proportion increases. No combination of previously assigned anionic BnHm species (including MgB12H12 and Mg(B3H8)2) can account for the average composition of the unknown proportion of the sample. This is supported by FTIR spectra showing an absence of terminal B–H resonances in the 2500 cm–1 region that are present for B12H12 and B3H8 anionic species. Our combined analysis strongly indicates the presence of as yet unidentified Mg–B–H phase(s) in postmelted decomposed Mg(BH4)2 samples.
... are a few scattered studies of NaNH 2 -containing systems such as NaNH 2 −NaBH 4 ,(12, 17 ...... more ... are a few scattered studies of NaNH 2 -containing systems such as NaNH 2 −NaBH 4 ,(12, 17 ... Mg(NH 2 ) 2 and NaMgH 3 as intermediary phases with the overall decomposition reaction being ... in a 1:1 ratio, the system was shown to undergo a dehydrogenation process according ...
The thermodynamic properties of magnesium hydride nanoparticles have been investigated by hydroge... more The thermodynamic properties of magnesium hydride nanoparticles have been investigated by hydrogen decomposition pressure measurements using the Sieverts technique. A mechanochemical method was used to synthesize MgH(2) nanoparticles (down to approximately 7 nm in size) embedded in a LiCl salt matrix. In comparison to bulk MgH(2), the mechanochemically produced MgH(2) with the smallest particle size showed a small but measurable decrease in the decomposition reaction enthalpy (DeltaH decrease of 2.84 kJ/mol H(2) from DeltaH(bulk) = 74.06 +/- 0.42 kJ/mol H(2) to DeltaH(nano) = 71.22 +/- 0.49 kJ/mol H(2)). The reduction in DeltaH matches theoretical predictions and was also coupled with a similar reduction in reaction entropy (DeltaS decrease of 3.8 J/mol H(2)/K from DeltaS(bulk) = 133.4 +/- 0.7 J/mol H(2)/K to DeltaS(nano) = 129.6 +/- 0.8 J/mol H(2)/K). The thermodynamic changes in the MgH(2) nanoparticle system correspond to a drop in the 1 bar hydrogen equilibrium temperature (T(1 bar)) by approximately 6 degrees C to 276.2 +/- 2.4 degrees C in contrast to the bulk MgH(2) system at 281.8 +/- 2.2 degrees C. The reduction in the desorption temperature is less than that expected from theoretical studies due to the decrease in DeltaS that acts to partially counteract the effect from the change in DeltaH.
Concerns over green house gas emissions and their climate change effects have lead to a concerted... more Concerns over green house gas emissions and their climate change effects have lead to a concerted effort into environmental friendly technologies. One such emphasis has been on the implementation of the hydrogen economy. There are four major impediments to the implementation of a hydrogen economy: hydrogen production, distribution, storage and conversion. This thesis is focused on exploring the hydrogen storage problem. Hydrogen can be stored by a wide range of methods. One of these methods involves using a secondary material that stores hydrogen by either physisorbing hydrogen onto its surfaces or by reacting with it to form a new compound. Of the wide variety of materials that can interact with hydrogen, three different materials were chosen; (1) nano-structured materials of high surface area; mesoporous silica (MCM-41) and titanate nanotubes, and (2) hydrides of Ti-Mg-Ni alloys. Results of the hydrogen on mesoporous silica (MCM-41) showed 1 wt.% H[subscript]2 to a maximum of 2 wt...
One of the limitations to the widespread use of hydrogen as an energy carrier is its storage in a... more One of the limitations to the widespread use of hydrogen as an energy carrier is its storage in a safe and compact form. Herein, recent developments in effective high-capacity hydrogen storage materials are reviewed, with a special emphasis on light compounds, including those based on organic porous structures, boron, nitrogen, and aluminum. These elements and their related compounds hold the promise of high, reversible, and practical hydrogen storage capacity for mobile applications, including vehicles and portable power equipment, but also for the large scale and distributed storage of energy for stationary applications. Current understanding of the fundamental principles that govern the interaction of hydrogen with these light compounds is summarized, as well as basic strategies to meet practical targets of hydrogen uptake and release. The limitation of these strategies and current understanding is also discussed and new directions proposed.
ABSTRACT A simplified techno-economic model has been used as a screening tool to explore the fact... more ABSTRACT A simplified techno-economic model has been used as a screening tool to explore the factors that have the largest impact on the costs of using metal hydrides for concentrating solar thermal storage. The installed costs of a number of paired metal hydride concentrating solar thermal storage systems were assessed. These comprised of magnesium-based (MgH2, Mg2FeH6, NaMgH3, NaMgH2F) high-temperature metal hydrides (HTMH) for solar thermal storage and Ti1.2Mn1.8H3.0 as the low-temperature metal hydride (LTMH) for hydrogen storage. A factored method approach was used for a 200 MWel power plant operating at a plant capacity factor (PCF) of 50% with 7 hours of thermal storage capacity at full-load. In addition, the hydrogen desorption properties of NaMgH2F have been measured for the first time. It has a practical hydrogen capacity of 2.5 wt% (2.95 wt% theoretical) and desorbs hydrogen in a single-step process above 478 oC and in a two-step process below 478 oC. In both cases the final decomposition products are NaMgF3, Na and Mg. Only the single-step desorption is suitable for concentrating solar thermal storage applications and has an enthalpy of 96.8 kJ mol-1 H2 at the midpoint of the hydrogen desorption plateau. The techno-economic model showed that the cost of the LTMH, Ti1.2Mn1.8H3.0, is the most significant component of the system and that its cost can be reduced by increasing the operating temperature and enthalpy of hydrogen absorption in the HTMH that, in turn, reduces the quantity of hydrogen required in the system for an equivalent electrical output. The result is that, despite the fact that the theoretical thermal storage capacity of NaMgH2F (1416 kJ kg-1) is substantially lower than the theoretical values for MgH2 (2814 kJ kg-1), Mg2FeH6 (2090 kJ kg-1) and NaMgH3 (1721 kJ kg-1), its higher enthalpy and operating temperature leads to the lowest installed cost of the systems considered. A further decrease in cost could be achieved by utilizing metal hydrides with yet higher enthalpies and operating temperatures or by finding a lower cost option for the LTMH.
ABSTRACT The addition of Group IV elements of Si, Ge or Sn to Mg-based hydrides has led to the su... more ABSTRACT The addition of Group IV elements of Si, Ge or Sn to Mg-based hydrides has led to the successful destabilisation of MgH2 or NaMgH3, resulting in hydrogen release at lower temperatures. This is the first time a direct comparison has been made with all the samples prepared and characterised using identical conditions. Pure MgH2 desorbs hydrogen at a pressure of 1 bar at 282 °C, a temperature too high for typical mobile applications. The addition of Group IV metals to MgH2 causes the formation of intermetallic compounds (Mg2Si, Mg2Ge and Mg2Sn) upon hydrogen release. Theoretical calculations show promising thermodynamic equilibrium conditions for these systems. Experimentally, these conditions were difficult to achieve, however, hydrogen desorption results show that Ge has the most significant effect in allowing low temperature hydrogen release, followed by Sn, then Si. It was found that Si also has a beneficial effect on NaMgH3, reducing the desorption temperature.
ABSTRACT Aluminium sulphide (Al2S3) is predicted to effectively destabilise sodium aluminium hydr... more ABSTRACT Aluminium sulphide (Al2S3) is predicted to effectively destabilise sodium aluminium hydride (NaAlH4) in a single-step endothermic hydrogen release reaction. The experimental results show unexpectedly complex desorption processes and a range of new sulphur containing hydrogen storage materials have been observed. The NaAlH4–Al2S3 system releases a total of 4.9 wt% of H2 that begins below 100 oC without the need for a catalyst. Characterisation via temperature programmed desorption, in situ synchrotron powder X-ray diffraction, ex situ x-ray diffraction, ex situ Fourier transform infrared spectroscopy and hydrogen sorption measurements reveal complex decomposition processes that involve multiple new sulphur-containing hydride compounds. The system shows partial H2 reversibility, without the need for a catalyst, with a stable H2 capacity of ~1.6 wt% over 15 cycles in the temperature range of 200 oC to 300 oC. This absorption capacity is limited by the need for high H2 pressures (>280 bar) to drive the absorption process at the high temperatures required for reasonable absorption kinetics. The large number of new phases discovered in this system suggests that destabilisation of complex hydrides with metal sulphides is a novel but unexplored research avenue for hydrogen storage materials.
ABSTRACT An ordered mesoporous carbon scaffold (CMK-1) has been synthesized and infiltrated with ... more ABSTRACT An ordered mesoporous carbon scaffold (CMK-1) has been synthesized and infiltrated with NaAlH4 nanoparticles by solvent- and melt-infiltration techniques. Small angle X-ray scattering (SAXS), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission Electron Microscopy (TEM) and energy dispersive spectroscopy (EDS) are used to characterize the structure, composition and morphology before and after thermal treatment. This study illuminates some of the problems that can be associated with nanoconfinement of hydrogen storage materials including scaffold contamination, residual solvent contamination, sample morphology changes after heating, and other factors that can be detrimental to the application of these systems. Of particular interest is the expulsion of NaAlH4 decomposition products from the scaffold after heating beyond its melting point under vacuum. This results in the surface of mesoporous carbon particles having arrays of multi-micron-long Al filaments that are >100 nm in diameter. Copyright
Physical chemistry chemical physics : PCCP, Jan 14, 2013
The thermal decomposition of anhydrous Pa3[combining macron] Li2B12H12 was studied in situ by hig... more The thermal decomposition of anhydrous Pa3[combining macron] Li2B12H12 was studied in situ by high resolution synchrotron X-ray diffraction. A first-order phase transition can be observed at 355 °C where the unit cell volume expands by ca. 8.7%. The expanded β-Li2B12H12 polymorph simultaneously decomposes to a hydrogen poor γ-Li2B12H12-x phase. Expansion of the unit cell across the discontinuity is consistent with reorientational motion of B12H12(2-) anions, and the presence of a frustrated Li(+) lattice indicating Li ion conduction.
Dalton transactions (Cambridge, England : 2003), Jan 21, 2014
Rare earth metal borohydrides have been proposed as materials for solid-state hydrogen storage be... more Rare earth metal borohydrides have been proposed as materials for solid-state hydrogen storage because of their reasonably low temperature of decomposition. New synthesis methods, which provide halide-free yttrium and gadolinium borohydride, are presented using dimethyl sulfide and new solvates as intermediates. The solvates M(BH4)3S(CH3)2 (M = Y or Gd) are transformed to α-Y(BH4)3 or Gd(BH4)3 at ~140 °C as verified by thermal analysis. The monoclinic structure of Y(BH4)3S(CH3)2, space group P2₁/c, a = 5.52621(8), b = 22.3255(3), c = 8.0626(1) Å and β = 100.408(1)°, is solved from synchrotron radiation powder X-ray diffraction data and consists of buckled layers of slightly distorted octahedrons of yttrium atoms coordinated to five borohydride groups and one dimethyl sulfide group. Significant hydrogen loss is observed from Y(BH4)3 below 300 °C and rehydrogenation at 300 °C and p(H2) = 1550 bar does not result in the reformation of Y(BH4)3, but instead yields YH3. Moreover, composit...
ABSTRACT We have studied the complex decomposition mechanism of cubic γ-Mg(BH4)2 (Ia3̅d, a = 15.7... more ABSTRACT We have studied the complex decomposition mechanism of cubic γ-Mg(BH4)2 (Ia3̅d, a = 15.7858(1) Å) by in-situ synchrotron X-ray diffraction, temperature-programmed desorption, visual observation of the melt, and Fourier transform infrared (FTIR) spectroscopy. The decomposition and release of hydrogen proceeds through eight distinct steps, including two polymorphic transitions before melting, with a new ε-Mg(BH4)2 phase at ca. 150 °C. After melting, strong changes in sample color from yellow to brown to gray are consistent with the unknown Mg–B–H phase(s) (that diffract with high d-spacing halos) in the sample changing from an average composition of MgB2H5.3 at 325 °C, to MgB2.9H3.2 at 350 °C, and to MgB4.0H3.7 by 450 °C. From 350 to 450 °C, the crystalline Mg proportion increases. No combination of previously assigned anionic BnHm species (including MgB12H12 and Mg(B3H8)2) can account for the average composition of the unknown proportion of the sample. This is supported by FTIR spectra showing an absence of terminal B–H resonances in the 2500 cm–1 region that are present for B12H12 and B3H8 anionic species. Our combined analysis strongly indicates the presence of as yet unidentified Mg–B–H phase(s) in postmelted decomposed Mg(BH4)2 samples.
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Papers by Drew Sheppard