Magnesium alloy-graphite composites with tailored heat conduction properties for hydrogen storage applications

Melt-spun magnesium alloys that contain catalytically active constituents have become attractive hydrogen storage materials due to their ultra-fine and homogeneous microstructure and their excellent (de-)hydrogenation characteristics. However, their heat conduction properties have to be improved for practical applications. For this purpose, composites of melt-spun magnesium alloys and expanded natural graphite (ENG) were examined in this work. Melt-spun flakes were mixed with different amounts of up to 25.5 wt.% ENG. These mixtures were compacted to cylindrical pellets using compaction pressures up to 600 MPa. For comparison, pellets of pure magnesium hydride and ENG were equally processed. All sets of specimens were investigated regarding their thermal conductivities in radial and axial direction, their microstructure and phase fractions. It was found that the heat transfer characteristics can be tailored in a wide range, e.g. the thermal conductivity of magnesium alloy-ENG compacts were tuned from 1 up to 47 W m⁻¹ K⁻¹. For the system MgH₂-ENG, the thermal conductivity can be adjusted from 1 up to 43 W m⁻¹ K⁻¹. Therefore, a hydrogen storage material with homogeneous heat transfer properties can be anticipated which only slightly depend on the hydrogenated fraction.     

Bounding material properties for automotive storage of hydrogen in metal hydrides for low-temperature fuel cells

Metal hydride material properties required for on-board hydrogen storage for use with automotive polymer electrolyte fuel cell systems are discussed. Thermodynamic relationships between enthalpy and entropy of sorption are determined such that the storage system can be thermally integrated with the fuel cell system and be refueled at reasonable H₂ supply pressures of 50–200 atm. Simple criteria are developed for specifying minimum discharge kinetic rates needed to satisfy hydrogen demand on automotive duty cycles. Simple criteria are also developed for specifying minimum charge kinetic rates needed to refuel metal hydride tanks in reasonable time. Accessible intrinsic capacity and bulk density of the metal hydride are determined for the storage system to achieve system level targets for gravimetric and volumetric capacities. Based on these analyses, it is recommended that the storage media properties be measured on samples prepared by mixing the metal hydride with a high thermal conductivity material, and compacted to 600 kg m⁻³ bulk density. The compact should have a minimum effective thermal conductivity of 8.5 W m⁻¹ K⁻¹.     

Heat transfer trait simulation of H finned tube in ventilation methane oxidation steam generator for hydrogen production

With the steam obtained by the energy released from ventilation air methane oxidation, the hydrogen production through gasification method is considered more commercial. In order to constrain the steam parameter fluctuation, the shunt honeycomb ceramics are adopted to fill between the heat exchange tubes. However, transient heat transfer characteristics of this kind of heat exchanger have not been fully studied. This paper carried out a numerical simulation study on the transient heat transfer characteristics of H finned tube under periodic reverse-flow conditions. Results show that the existence of shunt honeycomb ceramics enhances the effect of radiation. Gas flow direction reversing destructs the original boundary layer, achieving a sudden rise of the convective heat flux in the new upstream. It takes about 12s to form a new relative stable boundary layer. The apparent heat transfer coefficient achieves a maximum of 108.77 W m⁻² K⁻¹ and an average of 99.1 W m⁻² K⁻¹.     

Metal (boro-) hydrides for high energy density storage and relevant emerging technologies

The current energy transition imposes a rapid implementation of energy storage systems with high energy density and eminent regeneration and cycling efficiency. Metal hydrides are potential candidates for generalized energy storage, when coupled with fuel cell units and/or batteries. An overview of ongoing research is reported and discussed in this review work on the light of application as hydrogen and heat storage matrices, as well as thin films for hydrogen optical sensors. These include a selection of single-metal hydrides, Ti–V(Fe) based intermetallics, multi-principal element alloys (high-entropy alloys), and a series of novel synthetically accessible metal borohydrides. Metal hydride materials can be as well of important usefulness for MH-based electrodes with high capacity (e.g. MgH₂ ~ 2000 mA h g⁻¹) and solid-state electrolytes displaying high ionic conductivity suitable, respectively, for Li-ion and Li/Mg battery technologies. To boost further research and development directions some characterization techniques dedicated to the study of M-H interactions, their equilibrium reactions, and additional quantification of hydrogen concentration in thin film and bulk hydrides are briefly discussed.     

Effects of particle sizes on methanol steam reforming for hydrogen production in a reactor heated by waste heat

This paper reports the effects of particle sizes on methanol steam reforming for hydrogen production in a reactor heated by waste heat. The unsteady model was set up, which has been applied to investigate the effects of particle sizes (1.77 mm–14.60 mm) on particle temperature, heat transfer quantity, overall coefficient of heat-transfer, etc. The heat transfer performance of waste heat recovery heat exchanger is improved when the particle size increases, which is conducive to increase hydrogen production. The particle temperature change rate, the specific enthalpy change rate, the moving velocity of the maximum heat release rate particle, the contribution rate of solid phases, the heat release rate and the overall coefficient of heat-transfer increase, but the effective time of heat transfer decreases. When the particle size increases from 1.77 mm to 14.60 mm, the solid phase average contribution rate increases from 89.43% to 94.03%, the overall coefficient of heat-transfer increases from 1.39 W m⁻² K⁻¹ to 13.41 W m⁻² K⁻¹, the heat release rate increases from 48.9% to 99.9% and the effective time of heat transfer reduces from 48 h to 6.7 h.     

Spatiotemporal variability of ground thermal properties in glacial sediments and implications for horizontal ground heat exchanger design

Thorough characterization of the spatiotemporal variability in soil thermal properties can facilitate better designs for horizontal geothermal heat pump (HGHP) systems by reducing ground heat exchanger (GHEX) costs. Results are presented from a new monitoring network installed across a range of glaciated terrains in Indiana (USA), including the first known observations of the dynamic range of thermal conductivity that occurs at the depth of horizontal GHEX installations. In situ thermal conductivity data can vary significantly on a seasonal basis in coarse-grained outwash sediments (0.8–1.4 W m⁻¹ K⁻¹), whereas clay- and silt-dominated moraine sediments have a dampened seasonal range within 10% of the annual mean. Thermal conductivity across the network ranges from 0.8 to 2.0 W m⁻¹ K⁻¹ depending on soil parent material, climatic setting, and particularly, soil-moisture variability. Results indicate that the standard industry practice to estimate thermal properties from soil type often leads to suboptimal GHEX design (i.e., GHEX design lengths were 44–52% longer than necessary to meet performance specifications). This research suggests that expanding the characterization of soil thermal properties in specific settings where HGHPs are targeted will improve understanding of the dynamic aspects of ground heat exchange and lead to more optimal HGHP system designs.     

Effective thermal conductivity of MgH2 compacts containing expanded natural graphite under a hydrogen atmosphere

Expanded natural graphite (ENG) was added to enhance the effective thermal conductivity of MgH₂, which is one of the important parameters in the design of MgH₂-based hydrogen storage tanks. Cylindrical MgH₂ compacts containing up to 20 wt% ENG flakes with various average sizes (20, 50, 200, 350 and 1200 μm) were fabricated to measure the effective thermal conductivity of MgH₂–ENG mixtures. The radial direction effective thermal conductivity of the compacts was measured under a hydrogen atmosphere up to 70 bar. The conductivity was significantly enhanced by the addition of ENG flakes, reaching 9.3 W m⁻¹ K⁻¹ at 20 wt% ENG at 1 bar of hydrogen. It was observed that hydrogen pressure and the size of ENG flakes influenced the conductivity together with the amount of ENG. As hydrogen pressure increased up to 20 bar, the conductivity continued to increase. On the other hand, the conductivity very slowly increased above 20 bar, exhibiting a saturation tendency. It relatively rapidly increased with increasing average flake size up to 200 μm and then gradually decreased with further increasing size up to 1200 μm, exhibiting the maximum value at an average flake size of 200 μm. This trend might be determined by the competition between the thermal resistance at ENG/MgH₂ interfaces and the formation of conductive networks of ENG flakes.     

Study on catalytic effect and mechanism of MOF (MOF = ZIF-8, ZIF-67, MOF-74) on hydrogen storage properties of magnesium

Using a deposition-reduction method, Mg/MOF nanocomposites were prepared as composites of Mg and metal-organic framework materials (MOFs = ZIF-8, ZIF-67 and MOF-74). The addition of MOFs can enhance the hydrogen storage properties of Mg. For example, within 5000 s, 0.6 wt%, 1.2 wt%, 2.7 wt%, 3.7 wt% of hydrogen were released from Mg, Mg/MOF-74, Mg/ZIF-8, Mg/ZIF-67, respectively. Activation energy values of 198.9 kJ mol⁻¹ H₂, 161.7 kJ mol⁻¹ H₂, 192.1 kJ mol⁻¹ H₂ were determined for the Mg/ZIF-8, Mg/ZIF-67, Mg/MOF-74 hydrides, which are 6 kJ mol⁻¹ H₂, 43.2 kJ mol⁻¹ H₂, and 12.8 kJ mol⁻¹ H₂ lower than that of Mg hydride, respectively. Moreover, the cyclic stability characterizing Mg hydride was significantly improved when adding ZIF-67. The hydrogen storage capacity of the Mg/ZIF-67 nanocomposite remained unchanged, even after 100 cycles of hydrogenation/dehydrogenation. This excellent cyclic stability may have resulted from the core-shell structure of the Mg/ZIF-67 nanocomposite.     

Selection of metal hydrides-based thermal energy storage: Energy storage efficiency and density targets

Thermo-chemical energy storage based on metal hydrides has gained tremendous interest in solar heat storage applications such as concentrated solar power systems (CSP) and parabolic troughs. In such systems, two metal hydride beds are connected and operating in an alternative way as energy storage or hydrogen storage. However, the selection of metal hydrides is essential for a smooth operation of these CSP systems in terms of energy storage efficiency and density. In this study, thermal energy storage systems using metal hydrides are modeled and analyzed in detail using first law of thermodynamics. For these purpose, four conventional metal hydrides are selected namely LaNi₅, Mg, Mg₂Ni and Mg₂FeH₆. The comparison of performance is made in terms of volumetric energy storage and energy storage efficiency. The effects of operating conditions (temperature, hydrogen pressure and heat transfer fluid mass flow rates) and reactor design on the aforementioned performance metrics are studied and discussed in detail. The preliminary results showed that Mg-based hydrides store energy ranging from 1.3 to 2.4 GJ m^?3 while the energy storage can be as low as 30% due to their slow intrinsic kinetics. On the other hand, coupling Mg-based hydrides with LaNi₅ allow us to recover heat at a useful temperature above 330 K with low energy density ca.500 MJ m^?3 provided suitable operating conditions are selected. The results of this study will be helpful to screen out all potentially viable hydrides materials for heat storage applications.     

Performance prediction of a coupled metal hydride based thermal energy storage system

The present study discusses the thermodynamic compatibility criteria for the selection of metal hydride pairs for the application in coupled metal hydride based thermal energy storage systems. These are closed systems comprising of two metal hydride beds – a primary bed for energy storage and a secondary bed for hydrogen storage. The performance of a coupled system is analyzed considering Mg₂Ni material for energy storage and LaNi₅ material for hydrogen storage. A 3-D model is developed and simulated using COMSOL Multiphysics® at charging and discharging temperatures of 300 °C and 230 °C, respectively. The LaNi₅ bed used for hydrogen storage is operated close to ambient temperature of 25 °C. The results of the first three consecutive cycles are presented. The thermal storage system achieved a volumetric energy storage density of 156 kWh m⁻³ at energy storage efficiency of 89.4% during third cycle.     

Measurement and analysis of effective thermal conductivity of LaNi5 and its hydride under different gas atmospheres

In this work, an ETC measurement cell based on the steady-state radial heat flow method was fabricated, and its reliability was validated by a commercial instrument. The ETCs of unactuated and activated LaNi₅ powder beds were measured under various filling gases in the pressure range from 0.1 to 1.5 MPa. The experimental results show that the ETC of activated LaNi₅ powder is much lower than that of the unactuated material due to the pulverization effect. The ETCs of unactuated and activated LaNi₅ powder in helium atmosphere lie in the ranges of 1.04–1.63 W m^?1 K^?1 and 0.49–0.85 W m^?1 K^?1, respectively. Furthermore, the ETC increases with the increasing pressure and thermal conductivity of filling gas. The effects of hydrogen absorption and desorption on the ETC were investigated by step-by-step reaction, which depend mainly on the hydrogen concentration and expansion/constriction of MH particles.     

Effect of design parameters on enhancement of hydrogen charging in metal hydride reactors

The effects of heat transfer mechanisms on the charging process in metal hydride reactors are studied under various charging pressures. Three different cylindrical reactors with the same base dimensions are designed and manufactured. The first one is a closed cylinder cooled with natural convection, the fins are manufactured around the second reactor and the third reactor is cooled with water circulating around the reactor. The temperatures of the reactor at several locations are measured during charging with a range of pressure of 1–10 bar. The third reactor shows the lowest temperature increase with the fastest charging time under all charging pressures investigated. The effective heat transfer coefficients of the reactors are also calculated according to the experimental results and they are found to be 5.5 ± 1 W m⁻² K⁻¹, 35 ± 2 W m⁻² K⁻¹ and 113 ± 1 W m⁻² K⁻¹, respectively. The experimental results showed that the charging of hydride reactors is mainly heat transfer dependent and the reactor with better cooling exhibits the fastest charging characteristics.     

Hydrogen storage system based on hydride materials incorporating a helical-coil heat exchanger

Metal hydrides offer the potential to store hydrogen at modest pressures and temperatures with high volumetric efficiencies. The process of charging hydrogen into a metal powder to form the hydride is exothermic. The heat released by the reaction must be removed quickly in order to maintain a rapid charging rate. An effective method for heat removal is to embed a heat exchanger within the metal hydride bed. Here, we investigate the effectiveness of a helical coil heat exchanger tube to remove the heat generated during the absorption process. This paper presents a three-dimensional mathematical model formulated in Ansys Fluent 12.1 to evaluate the transient heat and mass transfer in a cylindrical metal hydride tank embedded with a helical-coil cooling tube. We present results from a parametric study of hydrogen storage efficiency as a function of helical coil pitch and convective heat transfer coefficient (h) within the cooling tube. We also explore the effect of adding aluminum foam to enhance the thermal conductivity of the metal hydride. The parametric study reveals that the mass of stored hydrogen is less sensitive to the coil pitch when aluminum foam is added. It is also found that the absorption rate increases with h as expected, although the rate of improvement diminishes at high values of h. Results were examined at filling times of 3 and 6 min to draw conclusions about the overall effectiveness of this hydrogen storage system. At 3 min, it is found that the addition of 5% Al foam is optimal, and h = 1000 W/m²-K is sufficient to bring the metal hydride to saturation; under these conditions a non-dimensional pitch of 0.5 maximizes the hydrogen absorption. Adding Al foam beyond 5% does not improve volumetric efficiency as the Al foam begins to displace the active hydrogen-absorbing material.     

Remarkable isosteric heat of hydrogen adsorption on Cu(I)-exchanged SSZ-39

Hydrogen storage capacity on Cu(I)-exchanged SSZ-39 (AEI), -SSZ-13 (CHA) and Ultra stable-Y (US–Y, FAU) at temperatures between 279 K and 304 K are investigated. The gravimetric hydrogen storage capacity values reaching 83 μmol H₂ g⁻¹ (at 279 K and 1 bar) are found to be comparable with the highest adsorption capacity values reported on metal-organic frameworks. The volumetric hydrogen storage capacity values; on the other hand, are found to be more than three times of those reported on metal-organic frameworks (0.57 g/L on Cu(I)-SSZ-39 at 1 bar and 296 K vs. ca. 0.18 g/L on Co₂(m-dobdc) at 1 bar and 298 K (Kapelewski MT, Runčevski T, Tarver JD, Jiang HZH, Hurst KE, Parilla PA et al. Record High Hydrogen Storage Capacity in the Metal-Organic Framework Ni₂(m-dobdc) at Near-Ambient Temperatures. Chem Mater 2018; 30:8179–89)). The isosteric heat of adsorption values are calculated to be between 80 kJ mol⁻¹ and 49 kJ mol⁻¹ on Cu(I)-SSZ-39 and between 22 kJ mol⁻¹ and 15 kJ mol⁻¹ on Cu(I)-US-Y indicating H₂ adsorption mainly at Cu(I) cations located at the eight-membered rings on Cu(I)-SSZ-39 and at six-membered rings on Cu(I)-US-Y. Hydrogen adsorption experiments performed at 77 K showed higher adsorption capacity values for Cu(I)-SSZ-39 at 1 bar, but Cu(I)-US-Y showed potential for hydrogen storage at higher pressure values.     

Experimental study of powder bed behavior of sodium alanate in a lab-scale H2 storage tank with flow-through mode

Chemical hydrogen storage in complex hydrides offers the potential of high gravimetric storage densities compared to intermetallic hydrides, and is therefore a promising technology for mobile applications. The main challenge for mobile application is still the required high refuelling rate of the hydrogen storage tanks. Since hydrogen is bonded by an exothermal chemical reaction in complex hydrides, appropriate storage tanks require high heat transfer rates for the cooling of the tank. Hydride tanks that are state of the art rely on an indirect cooling and are additionally equipped with e.g. finns, foams, etc. to improve the heat transfer rate. For the present study, an improved laboratory tank, which allows for indirect as well as direct cooling by excess H₂ gas (flow-through mode), has been designed and built. This laboratory tank is filled with 87 g of NaAlH₄ (doped with 2 mol% CeCl₃) and equipped with 8 thermocouples as well as two pressure sensors. Experimental results presented in this paper show a significant influence of the cooling by gaseous excess H₂ on the flow-directional temperature profiles at the part of the reaction bed close to the inlet. Considering the overall conversion, this influence is rather small due to the low heat capacity flux (ρc_p)_H2. Furthermore, it is shown that changes in material properties, attributed to the effects of heat and mass transport as well as intrinsic reaction kinetics, can be measured and assessed by the temperature and pressure sensors. After about 10 complete charging and discharging cycles, the initial permeability K of the bed has decreased by 50% to 1.6·10⁻¹² m². In the same time, the initial thermal conductivity has increased by a factor of 1.3 to values reported in literature (0.67 Wm⁻¹ K⁻¹) and remains constant during further cycles. Additionally, it is observed that the reaction rate of the second absorption step improves, even after a total of 36 cycles.     

Modeling the kinetic behavior of the Li-RHC system for energy-hydrogen storage: (I) absorption

The Lithium–Boron Reactive Hydride Composite System (Li-RHC) (2 LiH + MgB₂/2 LiBH₄ + MgH₂) is a high-temperature hydrogen storage material suitable for energy storage applications. Herein, a comprehensive gas-solid kinetic model for hydrogenation is developed. Based on thermodynamic measurements under absorption conditions, the system's enthalpy ΔH and entropy ΔS are determined to amount to −34 ± 2 kJ∙mol H₂⁻¹ and −70 ± 3 J∙K⁻¹∙mol H₂⁻¹, respectively. Based on the thermodynamic behavior assessment, the kinetic measurements' conditions are set in the range between 325 °C and 412 °C, as well as between 15 bar and 50 bar. The kinetic analysis shows that the hydrogenation rate-limiting-step is related to a one-dimensional interface-controlled reaction with a driving-force-corrected apparent activation energy of 146 ± 3 kJ∙mol H₂⁻¹. Applying the kinetic model, the dependence of the reaction rate constant as a function of pressure and temperature is calculated, allowing the design of optimized hydrogen/energy storage vessels via finite element method (FEM) simulations.     

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg₂FeH₆ hydride coupled with the low temperature Na₃AlH₆ hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based on a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450 °C to 500 °C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m³, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m³).     

Microstructural evolution and hydrogen storage proprieties of melt-spun eutectic Mg76.87Ni12.78Y10.35 alloy with low hydrides formation/decomposition enthalpy

Ternary eutectic Mg_76.87Ni_12.78Y_10.35 (at. %) ribbons with mixed amorphous and nanocrystalline phases were prepared by melt spinning. The microstructures of the melt-spun, hydrogenated and dehydrogenated samples were examined and compared by X-ray diffraction and transmission electron microscopy. The amorphous structure transforms into a thermally stable nanocrystalline structure with a grain size of about 5 nm during hydrogen ab/desorption cycles. The Mg, Mg₂Ni and phases with Y in the melt-spun state transform into MgH₂, Mg₂NiH₄, Mg₂NiH_0.3, YH₂ and YH₃ after hydrogenation, and transform back to Mg, Mg₂Ni and YH₂ upon subsequent dehydrogenation. The reaction enthalpy (ΔH) and entropy (ΔS) of the higher plateau pressure corresponding to Mg₂Ni hydride formation are −53.25 kJ mol⁻¹ and −107.74 J K⁻¹ mol⁻¹, respectively. The amorphous/nanocrystalline structure effectively reduces the enthalpy and entropy of Mg₂Ni hydride formation, but has little effect on Mg. The activation energy for dehydrogenation of the hydrogenated ribbons is 69 kJ mol⁻¹. This suggests that Mg–Ni–Y with ternary eutectic composition can form an amorphous/nanocrystalline structure by melt spinning, and this nanostructure efficiently improves the thermodynamics and kinetics for hydrogen storage.     

Synergistic catalytic effects of ZIF-67 and transition metals (Ni,Cu, Pd,and Nb) on hydrogen storage properties of magnesium

MgTM/ZIF-67 nanocomposites were prepared by the deposition-reduction method using ZIF-67, MgCl₂, and TMCl_x (TM = Ni, Cu, Pd, Nb) as raw materials. The dehydrogenation activation energies of MgTM/ZIF-67 (TM = Ni, Cu, Pd, Nb) nanocomposites were calculated to be 115.4 kJ mol⁻¹ H₂, 115.7 kJ mol⁻¹ H₂, 113.6 kJ mol⁻¹ H₂, and 75.8 kJ mol⁻¹ H₂, respectively; hence, the MgNb/ZIF-67 nanocomposite manifested the best comprehensive hydrogen storage performance. The hydrogen storage capacity of the MgNb/ZIF-67 nanocomposite was hardly attenuated after the 100th hydrogen absorption-desorption cycle. The dehydrogenated enthalpies of MgH₂ and CoMg₂H₅ in MgNb/ZIF-67 hydride were calculated to be 72.4 kJ mol⁻¹ H₂ and 81.0 kJ mol⁻¹ H₂, respectively, which were lower than those of additive-free MgH₂ and Mg/ZIF-67. The improved hydrogen storage properties of MgNb/ZIF-67 can be ascribed to the CoMg₂–Mg(Nb) core-shell structure and the catalytic effects of NbH and niobium oxide nanocrystals.     

In situ characterization of metal hydride thermal transport properties

Thermal property characterization of a metal hydride was conducted in a high pressure hydrogen environment with a transient plane source apparatus. This apparatus was integrated with a pressure vessel to measure the effective thermal conductivity and the thermal diffusivity of non-reactive and activated metal hydrides in hydrogen pressures up to 275 bar and 253 bar, respectively. In a non-reactive oxidized condition, the effective thermal conductivity of Ti_1.1CrMn powder increased with hydrogen pressure from 0.8 to 1.6 W/m·K. For activated powder, effective thermal conductivity increased from 0.3 to 0.7 W/m·K with hydrogen pressure. It is postulated that the smaller particle size associated with the reactive condition caused the reduction in effective thermal conductivity. Also, the derived specific heat of the activated Ti_1.1CrMn increased with reaction progress by a factor of two, with a maximum value at the fully hydrided state.