Characterization of metal hydrides for thermal applications in vehicles below 0 °C

Metal hydrides promise great potential for thermal applications in vehicles due to their fast reaction rates even at low temperature. However, almost no detailed data is known in literature about thermochemical equilibria and reaction rates of metal hydrides below 0 °C, which, though, is crucial for the low working temperature levels in vehicle applications.Therefore, this work presents a precise experimental set-up to measure characteristics of metal hydrides in the temperature range of −30 to 200 °C and a pressure range of 0.1 mbar–100 bar. LaNi_4.85Al_0.15 and Hydralloy C5 were characterized. The first pressure concentration-isotherms for both materials below 0 °C are published. LaNi_4.85Al_0.15 shows an equilibrium pressure down to 55 mbar for desorption and 120 mbar for absorption at mid-plateau and −20 °C. C5 reacts between 580 mbar for desorption and 1.6 bar for absorption at −30 °C at mid-plateau.For LaNi_4.85Al_0.15, additionally reaction rate coefficients down to −20 °C were measured and compared to values of LaNi₅ for the effect of Al-substitution. The reaction rate coefficient of LaNi_4.85Al_0.15 at −20 °C is 0.0018 s⁻¹. The obtained data is discussed against the background of preheating applications in fuel cell and conventional vehicles.     

Thermal modeling of LmNi4.91Sn0.15 based solid state hydrogen storage device with embedded cooling tubes

A 2-D mathematical model is developed for predicting the minimum charging/discharging time of the metal hydride based hydrogen storage device by varying the number of cooling tubes embedded in it. This study is extended to 3-D mathematical model for predicting the hydriding and dehydriding characteristics of LmNi_4.91Sn_0.15 based hydrogen storage device with 60 embedded cooling tubes (ECT) using COMSOL Multiphysics 4.3. The performance of the hydrogen storage device during hydriding/dehydriding process is presented for different supply pressure (10–35 bar), hot fluid temperature (30–60 °C) and effective thermal conductivity of hydride bed (0.2–2.5 W/(m?K)). It is observed that the rate of heat transfer and the hydriding and dehydriding rates are enhanced when the number of ECT is increased from 24 to 70. For the reactor with 60 ECT, the rate of hydrogen absorption is rapid for the supply pressure of 35 bar and hydride bed effective thermal conductivity of 2.5 W/(m?K). The numerically predicted hydrogen storage capacity (wt%) and amount of hydrogen desorbed (wt%) are compared with experimental data and found a good accord between them.     

Measurement of thermodynamic properties of some hydrogen absorbing alloys

In this paper, the effect of hydrogen concentration on the reaction enthalpies of some metal hydride alloys during hydriding and dehydring is presented. Pressure–concentration–temperature characteristics of the metal hydride alloys are measured under nearly isothermal condition during both absorption and desorption. Reaction enthalpies and entropies of LaNi₅, LaNi_4.7Al_0.3, LmNi_4.91Sn_0.15, Ti_0.99Zr_0.01V_0.43Fe_0.09Cr_0.05Mn_1.5 and MmCo_0.72Al_0.87Fe_0.04Ni_3.91 are estimated by constructing van't Hoff plots at different hydrogen concentrations. It is observed that the effect of hydrogen concentration on reaction enthalpies is more significant for the alloys having larger plateau slopes. At the initial stage of hydrogenation, metal hydrides are found to have larger reaction enthalpies which decrease gradually by about 5–15% at the end of the hydrogen absorption. At any given temperature, desorption enthalpies of LaNi₅, LmNi_4.91Sn_0.15, MmCo_0.72Al_0.87Fe_0.04Ni_3.91, LaNi_4.7Al_0.3 and Ti_0.99Zr_0.01V_0.43Fe_0.09Cr_0.05Mn_1.5 are found to be higher by about 5, 8, 10, 28 and 32% than their respective absorption enthalpies. Reaction enthalpies of the selected metal hydride alloys are expressed as a function of hydrogen concentration by a fourth order polynomial equation obtained from fitting with the experimental data.     

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.     

Open and closed metal hydride system for high thermal power applications: Preheating vehicle components

Many vehicle components operate at temperatures above ambient conditions. At cold start, most of the pollutants are produced and lifespan is reduced. Thermochemical energy storage with high power density could prevent these disadvantages. In order to investigate achievable power densities of a thermochemical energy storage at technically relevant boundary conditions, a laboratory scale device using metal hydrides (LaNi_4.85Al_0.15 and C5^®) is designed and preheating operation modes (open and closed) are analyzed. The impact of the ambient temperature (from ?20 to +20 °C), a s well as other influencing factors on the thermal power output such as heat transfer flow rate, regeneration temperature and pressure conditions are investigated. The experiments proved the suitability of the reactor design and material selection for the considered application boundary conditions. For the coupled reaction (closed system), the ambient temperature has the greatest influence on the thermal power with decreasing values for lower temperatures. Here, values between 0.6 kW/kg_MH at ambient temperature of ?20 °C and 1.6 kW/kg_MH at 20 °C, at otherwise same conditions, were reached. If hydrogen can be supplied from a pressure tank (open system), the supply pressure in relation to equilibrium pressure at the considered ambient temperature has to be large enough for high thermal power. At ?20 °C, 1.4 kW/kg_MH at a supply pressure of 1.5 bar and 5.4 kW/kg_MH at a hydrogen pressure of 10 bar were reached.     

Dynamic model and experimental results of a thermally driven metal hydride cooling system

This paper presents a dynamic model and experimental results of a metal hydride cooling system based on a coupled pair of reactors: a hot reaction bed (alloy LmNi_4.91Sn_0.15) and a cold reaction bed (Ti_0.99Zr_0.01V_0.43Fe_0.09Cr_0.05Mn_1.5). The driving power is waste heat removed at high temperature (130 °C). Metal hydride reactors can have interesting applications in thermal storage systems, refrigeration and heat pumps. The experimental setup is described, as well as the governing equations of the model. Correlations are used for the relationship between the equilibrium pressure, hydrogen concentration and temperature. An innovative approach is used for the modelling of hysteresis. The simulation results are compared and validated with experimental measurements during dynamic refrigeration cycles.     

Experimental results of a compact thermally driven cooling system based on metal hydrides

In this paper a detailed experimental analysis of a metal hydride based cooling system is presented. For the high temperature side an AB₅ type alloy (LmNi_4.91Sn_0.15) was chosen, whereas an AB₂ type alloy (Ti_0.99Zr_0.01V_0.43Fe_0.09Cr_0.05Mn_1.5) is used for the low temperature side. Due to very good heat and also mass transfer characteristics (among others, large heat transfer surface area) of the utilized capillary tube bundle reaction bed, very short half-cycle times in the order of 100 s have been reached. Consequently, the specific cooling power of the system is up to 780 W per kg desorbing metal hydride – depending on the temperature boundary conditions. The system was experimentally analyzed for different cooling and ambient temperatures, whereas the heating temperature was fixed to 130 °C.     

Performance investigations of a single-stage metal hydride heat pump

This paper discusses the performance investigations of a single-stage metal hydride heat pump (SS-MHHP) working with five different alloy pairs, namely, MmNi_4.6Al_0.4/MmNi_4.6Fe_0.4, LaNi_4.61Mn_0.26Al_0.13/La_0.6Y_0.4Ni_4.8Mn_0.2, LmNi_4.91Sn_0.15/Ti_0.99Zr_0.01V_0.43Fe_0.09Cr_0.05Mn_1.5, LaNi_4.6Al_0.4/MmNi_4.15Fe_0.85 and Zr_0.9Ti_0.1Cr_0.9Fe_1.1/Zr_0.9Ti_0.1Cr_0.6Fe_1.4. The performance of the system is predicted by solving the unsteady, two-dimensional coupled heat and mass transfer processes in metal hydride bed of cylindrical configuration using a fully implicit finite volume method. The influences of operating temperatures such as heat source (T_H), heat sink (T_M) and refrigeration (T_C) temperatures on the coefficient of performance (COP) and specific cooling power (SCP) of the system are presented. The predicted hydride bed temperature profiles are compared with the experimental data reported in the literature and a reasonably good agreement is observed between them. The optimum operating temperature ranges of each pair of alloys are suggested. For the selected operating temperatures, a maximum COP of 0.66 is predicted for Zr_0.9Ti_0.1Cr_0.9Fe_1.1/Zr_0.9Ti_0.1Cr_0.6Fe_1.4 hydride pair, while LmNi_4.91Sn_0.15/Ti_0.99Zr_0.01V_0.43Fe_0.09Cr_0.05Mn_1.5 hydride pair produces the highest SCP of 53.25 W/kg of total mass of the system.     

Experimental analysis of fast metal hydride reaction bed dynamics

In this paper an experimental investigation of main influencing parameters on the dynamics of a metal hydride reaction bed is presented. The metal hydride used in this work is LmNi_4.91Sn_0.15 and the applied reaction bed is based on a capillary tube bundle heat exchanger with a large heat transfer surface. Based on experimental investigations of the hydrogen distribution in the capillary tube bundle reaction bed a limitation of the reaction bed dynamics due to insufficient hydrogen transport can be excluded. However, it is shown that the desorption dynamics of the reaction bed can be limited by the intrinsic kinetics of the used AB₅ alloy.     

Development of a two-stage metal hydride system as topping cycle in cascading sorption systems for cold generation

Thermally driven sorption heat pumps compete to be an alternative to mechanically driven vapor compression heat pumps. They do not use CFC refrigerants and therefore have no ozone depletion potential and only a negligible global warming potential. However, their performance lacks behind, even if in the case of compression devices the efficiency of electricity generation is taken into account. The currently available sorption devices have a coefficient of performance (COP) for cooling of about 0.75 for single-effect systems and of 1.2 for double-effect systems. Since the temperatures and pressures under which sorption systems are operated differ widely, it has been suggested to combine sorption systems operating with different working pairs to form a cascading system, in which a topping cycle is producing cold and heat at a sufficiently high temperature level to be able to drive a bottoming cycle which also produces cold, thus increasing the COP.In this study, a two-stage metal hydride sorption device is investigated, which is used as a topping cycle in a cascading system. The system comprises the three metal hydrides LmNi_4.91Sn_0.15, LaNi_4.1Al_0.52Mn_0.38 and Ti_0.99Zr_0.01V_0.43Fe_0.09Cr_0.05Mn_1.5 in two reactors each. It is operated with a driving temperature of 310 °C, releasing heat for driving a bottoming cycle at a temperature of 125 °C and producing cold at a temperature of 2 °C. With a half-cycle time of 15 min and using the reaction enthalpies and the exchanged amount of hydrogen, the heat and cold output of the system can be determined. The total cold production is 1.8 kW and the heat generation is around 1.5 kW. The COP is in the range of 0.9 and the coefficient of heat amplification around 0.75. If a double-effect lithium bromide–water system with the above-mentioned COP is used as the bottoming cycle of the cascading system an overall COP of 1.8–2 is expected.     

Experimental studies on industrial scale metal hydride based hydrogen storage system with embedded cooling tubes

The present article reports the activation and testing of large scale metal hydride based hydrogen storage system (MHHSS) for industrial application. The metal hydride reactor is fabricated using SS316 material with 99 embedded cooling tube and filled with 40 kg of LaNi_4.7Al_0.3. The activation was carried out by successive absorption and desorption processes. In the third absorption cycle, MHHSS had absorbed 552.356 g of hydrogen to reach a maximum storage capacity of 1.4 wt% at 40 bar pressure and 30 °C temperature. The testing of MHHSS was carried out by varying H₂ supply pressure, absorption and desorption temperatures and heat transfer fluid (HTF) flow rate. It was observed that the supply pressure has significant effect on absorption rate, and the optimum supply pressure was observed in the range of 10–15 bar. Similarly, during the desorption cycle, optimum desorption temperature was found in the range of 80–90 °C. The optimum flow velocity for HTF was observed in the range of 20–30 lpm.     

Simulation of double-stage double-effect metal hydride heat pump

This paper presents the operational characteristics of a double-stage double-effect metal hydride heat pump (DSDE-MHHP) working with LaNi_4.1Al_0.52Mn_0.38/LmNi_4.91Sn_0.15/Ti_0.99Zr_0.01V_0.43Fe_0.09Cr_0.05Mn_1.5 as high/medium/low temperature alloys. The performances of the DSDE-MHHP are predicted by solving the transient, two-dimensional, conjugate heat and mass transfer characteristics between the paired metal hydride reactors of cylindrical configuration using the finite volume method (FVM). The designed operating temperatures chosen for the present analysis are 568, 361, 296, and 289 K as heat driven (T_D), heat rejection (T_H), heat sink (T_M) and refrigeration (T_C) temperatures, respectively. The variations in hydrogen concentrations, hydride equilibrium pressures, and temperatures within the hydride beds, and the heat exchange between the hydride beds with the heat transfer fluids are presented for a complete cycle. The operating cycle of a DSDE-MHHP is explained on dynamic pressure–concentration–temperature (PCT) plot. The variation of temperatures in the reactors during hydriding and dehydriding processes is compared with experimental data and a good agreement was observed between them. For given operating temperatures of 568/361/296/289 K, the average coefficient of performance (COP) and the specific cooling power (SCP) of the system are found to be 0.471 and 28.4 W/kg of total hydride mass, respectively.     

Performance analysis of LaNi5 added with expanded natural graphite for hydrogen storage system

This paper presents a comparative study of two cases of metal hydride hydrogen storage units working on (i) LaNi₅ (ii) Compacts of LaNi₅ incorporated with expanded natural graphite (ENG). It has been observed from the previous studies that the hydriding/dehydriding reactions eventually causes large strain changes, due to which the hydride forming metal alloys disintegrate and form a powder bed. Such reactor beds usually have a low thermal conductivity which minimizes the heat transfer phenomenon occurring during the absorption of hydrogen gas. Therefore, there is a need to implement heat augmentation methods to significantly enhance the thermal conductivity. The objective of this research is to present a 2-D numerical model using Finite Volume Method (FVM) and estimate the hydrogen storage performance of a cylindrical metal hydride bed for both the cases, i.e. powdered metal hydride bed and ENG compacts-based reactor bed at different values of inlet pressure and heat transfer fluid temperature. In this study, a detailed investigation on the absorption process reveals that reactor beds with compacted disks of LaNi₅ and ENG demonstrate an enhanced effective thermal conductivity and efficient mass transfer. The simulation results show that a remarkable improvement in the heat transfer and hydrogen storage capacity with reduced absorption time can be achieved by using LaNi₅ and ENG compacts. It was observed that the average reactor bed temperature dropped from 345.13 K to 337.37 K when the ENG based compacted disks was introduced into the reactor bed. Moreover, for supply pressure of 24 bar and fluid temperature of 293 K, the time taken to absorb hydrogen into the rector to achieve stabilized hydrogen storage capacity was estimated to be 446s and 232 s for the case of metal hydride and ENG compacts-based bed, respectively.     

Performance investigation of double-stage metal hydride based heat pump

In this paper, the performance investigation of a Double-Stage Double-Effect Metal Hydride Heat Pump (DSDE-MHHP) working with LaNi_4.1Al_0.52Mn_0.38, LmNi_4.91Sn_0.15 and Ti_0.99Zr_0.01V_0.43Fe_0.09Cr_0.05Mn_1.5 hydride alloys is presented. The effects of half cycle time (θ), hydride mass ratio (M_R), sensible heat exchange factor (?) and operating temperatures, viz. heat source (T_D), heat sink (T_M), and refrigeration (T_C) temperatures on the amount of hydrogen transferred between the paired reactors, coefficient of performance (COP) and specific cooling power (SCP) of the DSDE-MHHP system are investigated. For the present analysis the heat rejection temperature (T_H) is maintained constant at 373 K. Numerically predicted hydride bed temperatures are compared with experimental data and a good agreement is observed between them. It is observed from the numerical results that the COP and SCP of the DSDE-MHHP system increase with heat source and refrigeration temperatures, and decrease with heat sink temperature. For operating temperatures of 578, 373, 298 and 283 K (T_D, T_H, T_M and T_C), the average COP and SCP of the system are found to be 0.81 and 48.1 W/kg of total alloy mass, respectively.     

Polyetherimide-LaNi5 composite films for hydrogen storage applications

This study investigates the preparation of polyetherimide (PEI) – LaNi₅ composites films for hydrogen storage. Prior to the polymer addition, LaNi₅ was ball-milled at different conditions (250, 350, and 450 RPM) and annealed at 500 °C for 1 h under vacuum. The composites were produced with BM-LaNi₅-350 (PEI/LaNi₅-350) and annealed BM-LaNi₅-350 (PEI/LaNi₅-350-TT). Membranes were successfully produced through solvent casting assisted by an ultrasonic bath. The particles dispersion and the film morphology did not change after hydrogenation cycles. In the H₂ sorption experiments at 43 °C and 20 bar, the films stored H₂ without incubation time; both samples reached a capacity of ~0.6 wt%. The H₂ sorption kinetics of PEI/LaNi₅-350 was comparable to that of BM-LaNi₅-350, whereas PEI/LaNi₅-350-TT presented significantly slower kinetics. LaNi₅ oxidation was hindered by PEI, showing that it can be explored to improve metal hydrides air resistance. The results demonstrated that PEI films filled with LaNi₅ are promising materials for hydrogen storage.     

Studies on hydriding kinetics of some La-based metal hydride alloys

In this paper, the hydriding kinetics of LaNi₅, LaNi_4.7Al_0.3 and LmNi_4.91Sn_0.15 is presented. Experiments were carried out by maintaining the pressure ratio (supply pressure to equilibrium pressure at the mid-point of the pressure–concentration–isotherm) equal to 2 and by maintaining nearly isothermal reaction conditions. Two widely used reaction kinetics models, namely Johnson–Mehl–Avrami (JMA) model and Jander diffusion model (JDM) are considered for the analysis. Two JMA models are considered; in the first model, the order of the reaction is assumed as unit and in the second model, the rate constant is calculated by estimating the order by fitting the reaction kinetics data with a reaction kinetics equation. The activation energy and pre-exponential constants of the above-mentioned alloys are estimated by constructing the Arrhenius plot. Activation energies estimated from the different models are compared and the accurate values of activation energy for the different alloys are determined by comparing the reaction kinetics data obtained from the models with the experimental data. The rate-controlling step of the hydriding reaction is obtained for all the alloys investigated.     

Studies on 10kg alloy mass metal hydride based reactor for hydrogen storage

A 10 kg alloy mass metal hydride reactor, with LaNi₅ alloy was designed. Heat transfer enhacement in the reactor was achieved by including embedded cooling tubes and an external water jacket. Detailed parametric study has been carried to understand the performance of the system. The effect of both geometrical and operational parameters was studied in simulations. The optimized geometrical parameters were used for fabricating the reactor. Experimental studies were carried on the fabricated reactor. Absorption studies were carried out for different supply pressure and different cooling fluid temperatures. Storage capacity of 1.13 wt% was found in 1620 s at a supply pressure of 25 bar and with a flow rate of 20 LPM. Similarily, desorption studies were carried out for varying heat transfer fluid temperatures. Complete and fastest desorption was observed at 80 °C with the reaction completion time of 2700 s.