Metal Hydride Hydrogen Research Articles

Parametric Analysis of a Novel Array-Type Hydrogen Storage Reactor with External Water-Cooled Jacket Heat Exchange

Hydrogen energy is a green and environmentally friendly energy source, as well as an excellent energy carrier. Hydrogen storage technology is a key factor in its commercial development. Solid hydrogen storage methods represented by using metal hydride (MH) materials have good application prospects, but there are still problems of higher heat transfer resistance and slower hydrogen absorption and release rate as the material is applied to reactors. This study innovatively proposed an array-type MH hydrogen storage reactor based on external water-cooled jacket heat exchange, aiming to improve the heat transfer efficiency and absorption reaction performance, and optimize the absorption kinetics encountered in practical applications of LaNi5 hydrogen storage material in reactors. A mathematical model was built to compare the hydrogen absorption processes of the novel array-type and traditional reactors. The results showed that, with the same water-cooled jacket, the hydrogen absorption rate of the array-type reactor can be accelerated by 2.78 times compared to the traditional reactor. Because of the existence of heat transfer enhancement limits, the increase in the number of array elements and the flow rate of heat transfer fluid (HTF) has a limited impact on the absorption rate improvement of the array-type reactor. To break the limits, the hydrogen absorption pressure, as a direct driving force, can be increased. In addition, the increased pressure also increases the heat transfer temperature difference, thereby further improving heat transfer and absorption rate. For instance, at 3 MPa, the hydrogen absorption time can be shortened to 147 s.

Synthesis of silacycles via metal hydrogen atom transfer and radical-polar crossover mechanism

In this study, we have developed an efficient method for silacycle synthesis using metal hydride hydrogen atom transfer (MHAT) and radical-polar crossover (RPC) mechanism. Allylic silanols were synthesized via one-step condensation and then cyclized under mild conditions using N-fluoropyridinium tetrafluoroborate (Me3NFPY·BF4) as the oxidant under cobalt catalysis. This approach yielded five-, six-, and seven-membered silacycles with high selectivity, with the six-membered rings being the favored products. Density functional theory (DFT) calculations provided valuable insights into the reaction mechanisms and highlighted the role of ring strain in determining product selectivity. This study demonstrated the effectiveness of combining MHAT/RPC methodologies with silicon tethering, thus offering a robust platform for expanding the use of silicon-based strategies in synthetic chemistry.

Heat pipe for thermally coupled fuel cell and metal hydride as well as for cooling metal hydride hydrogen charging

ABSTRACT In this paper, a metal hydride (MH) canister and a PEM fuel cell are coupled using heat pipes to study the minimum number of heat pipes required, the operating range of the fuel cell, and the temperature change patterns of the MH. We account for temperature difference limitations between the fuel cell and the MH (∆T = 35–55 K) on the heat pipe dynamics, which has been neglected in previous similar studies. Since the hydrogen absorption rate of the MH canisters exhibits an initial increase followed by a decrease with increasing temperature, an analysis was conducted to select the appropriate heat pipe under different hydrogen filling pressures. This analysis ensured that the MH canisters remained at the optimal charging temperature (326 K) and achieved the maximum charging rate (6.64 slpm).

Towards standalone commercial buildings in the Mediterranean climate using a hybrid metal hydride and battery energy storage system

Given the critical role of hybrid energy storage systems in the building sector for enhancing renewable energy reliability and integration, this study examines the techno-economic feasibility of adopting a dual-level energy storage system for a PV-driven commercial building in the Mediterranean climate. The proposed system encompasses both hydrogen metal hydride and battery storage units. Aimed at off-grid electrification, the optimal component sizing of the hybrid system is identified by establishing a statistical optimization framework using the response surface methodology. Dynamic simulations of the hybrid system are performed through a TRNSYS model coupled with a numerical code that simulates the metal hydride system. Regarding optimal net-zero solutions, it is shown that the share of the direct PV electricity supply to end-use fluctuates within a limited range for all scenarios, namely between 57.7 and 60.5 %, while the share of each storage system varies distinctively in each solution. The results indicate a striking difference between scenarios in terms of economic aspects; differences of $ 19,791 and $ 32,621 are observed between the minimum and maximum values of the initial investment and life cycle cost, respectively. The levelized cost of electricity varies between 0.354 and 0.403 $/kWh, in which the case having the lowest payback period (10.8 years) demonstrates the lowest levelized cost of electricity too. Furthermore, an inverse relationship between the levelized cost of hydrogen and production rate is observed; the lowest levelized cost and the highest annual production are achieved in the scenario with the lowest BESS capacity and the highest electrolyzer power and hydrogen storage volume, which are equal to 5.77 $/kg and 304.7 kg H2/yr, respectively.

Harnessing the potential of acyl triazoles in bifunctional cobalt-catalyzed radical cross-coupling reactions

Persistent radicals facilitate numerous selective radical coupling reactions. Here, we have identified acyl triazole as a new and versatile moiety for generating persistent radical intermediates through single-electron transfer processes. The efficient generation of these persistent radicals is facilitated by the formation of substrate-coordinated cobalt complexes, which subsequently engage in radical cross-coupling reactions. Remarkably, triazole-coordinated cobalt complexes exhibit metal-hydride hydrogen atom transfer (MHAT) capabilities with alkenes, enabling the efficient synthesis of diverse ketone products without the need for external ligands. By leveraging the persistent radical effect, this catalytic approach also allows for the development of other radical cross-coupling reactions with two representative radical precursors. The discovery of acyl triazoles as effective substrates for generating persistent radicals and as ligands for cobalt catalysis, combined with the bifunctional nature of the cobalt catalytic system, opens up new avenues for the design and development of efficient and sustainable organic transformations.

Development of a high-pressure 700 bar metal hydride hydrogen compressor

HySA Systems and TF Design have recently developed a single-stage prototype high-pressure metal hydride hydrogen compressor (MHHC) which is able to compress hydrogen from 100 to >700 bar at the working temperatures from 20 to 150 °C, with estimated productivity about 1 Nm3/h. The MHHC comprises of two 2 m-long fibre-wound high-pressure MH containers developed by the authors earlier and assembled in two modules operating in a mode of a cyclic lower-pressure H2 absorption (on cooling) and high-pressure H2 desorption (on heating). The containers operate using a self-developed multicomponent C14 Laves type Ti–based AB2 intermetallic alloy. The article considers phase-structural and hydrogen sorption properties of the utilized metal hydride material, hydrogen compression performances of the metal hydride container, as well as layout and the expected performance characteristics of the compressor assembly.

Optimization of cold startup strategy with quasi 2-D model of metal hydride hydrogen storage with fuel cell

In this work, a novel cold startup strategy is presented for a large-scale metal hydride–fuel cell system. Due to the thermal requirement of the system, when the initial temperature of metal hydride and ambient air is low, the system cannot be started because the hydrogen pressure in the metal hydrides storage system is lower than the minimal pressure required by the fuel cell. The cold startup is achieved by maintaining a part of metal hydride storage at a target temperature and using coolant control to transfer heat to the remaining cold metal hydride storage upon operation of the fuel cells. The strategy is studied numerically and a novel Quasi-2-Dimensional approach is developed to describe heat transfer within metal hydrides and validated. By the proper selection of the value of the control variable, both fast startup and immediate uninterrupted fuel cell power supply are achieved. The effect of initial conditions on the startup process is studied and the strategy consumed 30 % less energy than the alternative without control. The proposed strategy is suitable and efficient for the cold startup of large-scale metal hydride-fuel cell systems.

Exploring hydrogen storage safety research by bibliometric analysis

The application of hydrogen energy is affected by the safety of hydrogen storage system. To grasp the current status of research and application in the research field of hydrogen storage safety and explore its research development trend, data analysis techniques, such as co-occurrence, co-citation, and burst detection, were adopted to conduct bibliometric analysis of the relevant literature. The study results show that the research hotspots of hydrogen storage safety mainly concentrate on six aspects: the stability of metal hydride hydrogen storage materials, the study of thermal management and stress relief in metal hydride reactors, the safety analysis of hydrogen fuel cells and hydrogen leakage monitoring, the analysis of leakage and explosion risks in hydrogen refueling stations, the study of filling pressure and temperature distribution in hydrogen storage tanks, and the study of safety issues in underground hydrogen storage. Mg-based hydride stability and underground hydrogen storage risk analyses are current research frontiers in hydrogen storage safety.

Synergetic enhancement of hydrogen concentration and heat transfer for triply periodic minimal surface based hydrogen storage reactor

Metal hydride hydrogen storage technology is considered a potential alternative energy and energy storage solution in promoting global economic decarbonization. However, the heat transfer coefficient between hydrogen storage materials and reactors is relatively low, which cannot meet the heat transfer and hydrogen storage requirements of the metal hydride tank. This study employs a triply periodic minimal surface (TPMS) based hydrogen storage reactor and design of experiments (DOE) to reveal the relationship between various parameters and their characteristics. The multi-physics coupling of fluid flow, heat transfer, chemical reactions, and stress in a metal hydride hydrogen storage reactor is also combined to promote the synergistic improvement of heat transfer and hydrogen storage efficiency. Numerical simulation results demonstrate that the hydrogen absorption volume fraction of tank equipped with TPMS is 0.926, which is significantly higher than that of conventional finned one. The absorption of hydrogen leads to volume expansion, resulting in a 30.61 % increase in expansion stress. Furthermore, the optimal hydrogen absorption volume fraction occurs at a temperature of 273.15 K, a pressure of 3.49 MPa, and a velocity of 5 m/s.

Performance optimization study on the thermal management system of proton exchange membrane fuel cell based on metal hydride hydrogen storage

To compare the performance differences between proton exchange membrane fuel cell (PEMFC), metal hydride tank (MHT) and heat exchanger (HX) coupling configurations and optimize thermal management methods, this study investigates and compares three coupling systems, PEMFC-MHT-HX series, PEMFC-HX-MHT series, and PEMFC-MHT|HX parallel system. Results reveal that, under controlled load variables, all three systems achieve an energy efficiency of 48.1 % at the maximum net power of 41.99 kW, increased by 16.93 % compared to standalone PEMFC. Exergy efficiencies of the systems show little differences, with values of 43.65 %, 43.38 %, and 43.51 %, respectively. The PEMFC-MHT-HX system exhibits the highest hydrogen outlet pressure, which is suitable for high-pressure applications. Conversely, the PEMFC-MHT|HX system enables flexible hydrogen supply regulation through decoupled control of hydrogen outlet pressure and flow. Increasing the MHT heat transfer coefficient can enhance the outlet pressure, but this effect diminishes beyond 1500 W/(m2·K). Sensitivity analysis identifies current and stack temperature as pivotal factors, emphasizing the necessity of precise current regulation and effective thermal management strategies. Additionally, the proportion of PEMFC waste heat recovered by the MHT decreases from 36.8 % to 29.0 % as the current load rises from 100 A to 400 A, indicating potential for alternative waste heat recovery devices over HX.

Energy management strategy for accurate thermal scheduling of the combined hydrogen, heating, and power system based on PV power supply

To solve the negative impact of renewable energy volatility on the power system, a combined hydrogen, heating and power system integrating alkaline water electrolysis, metal hydride hydrogen storage, and proton exchange membrane fuel cells (PEMFCs) is proposed. However, water electrolysis, hydrogen adsorption and PEMFC all generate heat, and how to use this heat is the key to improving the system efficiency. Therefore, four energy scheduling schemes are proposed in this study, aiming at making full use of waste heat to improve its energy utilization efficiency. The results show that the system heat is almost entirely utilized under the proposed four strategies. Meanwhile, the peak-valley strategy is more suitable for on-grid operation, and heat priority, peak clipping and load reduction strategy are more suitable for off-grid operation. Under the heat priority strategy, residual electricity and heat are the lowest. Under the peak clipping strategy, the current density of the PEMFC fluctuates the least and is maintained at 0.59 A cm−2 during the heat-led period. Under the load reduction strategy, during the heat-led period (5:00 p.m. ∼ 6:00 a.m.), the system electric power is lower than the power load for the shortest time, accounting for 23.93% of this operating duration.

Cobalt/Photoredox Dual-Catalyzed Cross-Radical Coupling of Alkenes via Hydrogen Atom Transfer and Homolytic Substitution.

Cobalt-catalyzed metal hydride hydrogen atom transfer (MHAT) in combination with photoredox catalysis has emerged as a powerful synthetic method, owing to its redox nature and applicability to various radical precursors. Herein, we describe a cross-radical coupling reaction under cobalt/photoredox dual catalysis. MHAT and homolytic substitution (SH2) processes enabled Markovnikov-selective hydrobenzylation of di/trisubstituted alkenes, affording products with a quaternary carbon center in a redox-neutral manner.

Cyclization by metal-catalyzed hydrogen atom transfer/radical-polar crossover

Catalytic transformation of alkenes via the metal-hydride hydrogen atom transfer (MHAT) mechanism has notably advanced synthetic organic chemistry. This review focuses on MHAT/radical-polar crossover (MHAT/RPC) conditions, offering a novel perspective on generating electrophilic intermediates and facilitating various intramolecular reactions. Upon using cobalt hydrides, the MHAT mechanism displayed exceptional chemoselectivity and functional group tolerance, making it invaluable for the construction of complex biologically relevant molecules under mild conditions. Recent developments have enhanced regioselectivity and expanded the scope of MHAT-type reactions, enabling the formation of cyclic molecules via hydroalkoxylation, hydroacyloxylation, and hydroamination. Notably, the addition of an oxidant to traditional MHAT systems enables the synthesis of rare cationic alkylcobalt(IV) complexes, bridging radical mechanisms to ionic reaction systems. This review culminates with examples of natural product syntheses and exploration of asymmetric intramolecular hydroalkoxylation, highlighting the ongoing challenges and opportunities for future research to achieve higher enantioselectivity. This comprehensive study revisits the historical evolution of the MHAT mechanism and provides the groundwork for further innovations in the synthesis of structurally diverse and complex natural products. 1 Introduction 2 Intramolecular hydroalkoxylation and hydroacyloxylation reactions 3 Intramolecular hydroamination reactions 4 Intramolecular hydroarylation reactions 5 Deprotective cyclization 6 Asymmetric intramolecular hydroalkoxylation

Development of Ti-Zr-Mn based AB2 type metal hydrides alloys for an 865 bar two-stage hydrogen compressor

This study reports the development of a new Ti-Zr-Mn-based AB2 type hydrogen storage alloys for a two-stage metal hydride hydrogen compressor (MHHC). The hydrogen storage alloys are designed to compress hydrogen from 35 to 865 bar within a temperature difference of 115 °C. High-pressure PCT measurements up to 700 bar were carried out to test the performance of the alloys. The alloys' hysteresis and the plateau slope were reduced by optimizing the composition. The introduction of fugacity correction into the Van't hoff equation reduces the deviation between calculation and actual pressure to 24 bar at a pressure above 350 bar. A precise relation between the Ti/Zr ratio and the desorption pressure is described and helps make a correct design of the alloy composition. The designed alloy shows looses less than 1% of the capacity over 3000 full cycles. The desorption plateau pressure of the alloy is constant within 92% during the whole cycling process. A 2 stages compressor working with two types of alloys offers compression with a temperature range between -20 and 95 °C for the refueling hydrogen vehicles up to 865 bar.

Modeling heat and mass transfer in metal hydride hydrogen storage systems: Impact of operating parameters and reactor geometry

This work introduces a transient 2D axis-symmetrical model for hydrogen absorption in a cylindrical LaNi5 reactor employing finite volume method with a fully implicit Euler's time integration scheme, coupling equations for heat, mass, and momentum transport. The validated model is used to investigate the impacts of pressure, cooling fluid temperature, and variations in reactor geometry and size on temperature and reacted fraction profiles. The findings reveal that the charging pressure affects both peak temperature and reaction kinetics, whereas cooling fluid temperature predominantly impacts the absorption kinetics. A comparative analysis of two models, one incorporating Darcy's velocity and one without, demonstrates that while Darcy's law introduces numerical instability in the coupled equations, its impact on the model outcomes is negligible. The effect of changing the non-homogeneous Neumann to Dirichlet boundary condition is also demonstrated to anticipate the utilization of phase change materials (PCM) instead of the cooling fluid.

Experimental and numerical investigations on synergistic coupling of metal hydride hydrogen storage systems with low-temperature proton exchange membrane fuel-cell

Hydrogen has emerged as a promising alternative for various energy needs, and metal hydride hydrogen systems offer significant potential due to their near-ambient working conditions and safe storage. This study presents experimental and numerical investigations on a lab-scale metal hydride fuel cell system to showcase its viability in addressing future energy demands. The experimental setup includes a 41-tube Metal Hydride (MH) reactor with an outer cooling jacket, containing 3.75 kg of La0.7Ce0.1Ca0.3Ni5. The output of the reactor is coupled to a 1 kW fuel cell, with controlled hydrogen discharge at temperatures ranging from 30 to 50 °C through numerical modelling. The study found that maintaining the reactor at 40 °C was sufficient to sustain the required bed pressure for a 1 kW fuel cell. Numerical simulations revealed that a 1 kW fuel cell operating at a current density of 0.8 A/cm2 and 50 °C rejected approximately 1.3 kW of waste heat. Moreover, 3.75 kg MH reactor could discharge hydrogen at a constant rate of 13 l/min for 36.3 min with just 125–225 W of heat input, highlighting the thermal coupling potential between these systems. The energy efficiency of the coupled MH-PEMFC system increased by 1.8 times to reach 49% at 50 °C. Additionally, the waste heat generated proved sufficient to provide the required endothermic heat to multiple MH reactors, with a single reactor utilizing only 16.3% of the total waste heat. This integrated system demonstrates promising efficiency and sustainability for future energy applications.

Analytical and experimental evaluation of LaNi5-xMx, where M = Fe, Mn, and Al hydrides for hydrogen compression applications

Metal Hydride Hydrogen Compressors (MHHC) will play a vital role in the hydrogen economy in the coming times. Developing a more efficient and optimized MHHC requires revisiting the existing materials and selecting the best-suited material. The current work compares LaNi5-xMx, where M = Fe, Mn, and Al hydrides, through a thermodynamic evaluation of the compressor's performance. The operating conditions have been chosen as 20 to 40 °C for absorption and 80 to 140 °C for desorption to provide a baseline for comparing the materials. The performance parameters include thermal efficiency, pressure ratio, and throughput (i.e. mass of hydrogen delivered per 100 g of hydride (wt.%)). The Pressure Concentration Isotherms (PCIs) are taken from the published literature, and the equilibrium pressures at the desired temperature conditions are calculated from the van't Hoff equation. LaNi4.8Al0.2 gives good performance throughout the studied temperature and pressure range. The throughput of LaNi4.8Al0.2 drops from 1.4 wt.% to around 1 wt.% at high absorption temperatures. A separate experimental study of LaNi4.8Al0.2 is documented where it is used in a prototype of MHHC, and its performance parameters are compared with the thermodynamic analysis. The reaction kinetics, throughput, pressure ratio, and efficiency are reported. A pressure ratio of 4.2 is achieved with an efficiency of 5.2 % at 3 bar supply pressure, and absorption and desorption temperatures of 30 and 140 °C, respectively.

Performance improvement of metal hydride hydrogen compressors using electromagnetic induction heating

While there are some hydrogen refueling stations (HRS) functioning in different parts of the world, their use is not widespread enough, primarily due to their expensive cost. Hydrogen compression is a main contributor to the capital and operation costs of the HRS. By improving H2 compression technology, it is possible to optimize the infrastructure for refueling with hydrogen in terms of cost and performance. The use of metal hydride hydrogen compressors (MHHCs), which have the potential to be inexpensive and have the ability to use waste heat and renewable energy sources for the H2 compression, is a promising solution to overcome this issue. The duration of the H2 compression cycle is nevertheless a serious challenge due to the metal hydride (MH) bed's low heat conductivity. As a heating technique to improve the performance of MHHCs, electromagnetic induction (EMI) is examined numerically for the first time in this work. The dynamic behavior of a two-stage MHHC with each MH reactor having an external heat exchanger and being ringed by a copper coil traversed by an alternating current is described by a two-dimensional mathematical model, which was established and successfully verified by the reference data. Numerical simulations were performed with the help of this model, and the findings showed that the EMI heating method is faster than the heat transfer fluid (HTF) heating technique. For instance, at a delivery temperature of 373 K and a supply pressure of 20 bar, it is possible to produce 106 NL H2 per kilogram of HPMH at a pressure of 97 bar with a 74 % shorter compression time than with the HTF heating technique.

CFD simulation of heat and mass transfer processes in a metal hydride hydrogen storage system, taking into account changes in the bed structure

CFD modelling of heat-and-mass transfer in metal hydride (MH) beds is an important step in the development and optimisation of MH reactors for hydrogen storage, compression and separation/purification. In the existing models, the mass conservation equation includes the density of solid in the non-hydrogenated (ρs) and hydrogen-saturated (ρss) states. To provide constant porosity of the MH bed during H2 absorption/desorption, assumption ρs<ρss is typically taken. However, this assumption contradicts to well-known fact that hydrogenation of hydride-forming alloys is accompanied by the expansion of crystal lattice of the metallic matrix and, therefore, by the decrease of the solid density by 15–25%.This work presents results of the modelling which takes this effect into account. The model assumes that the density of the MH changes linearly as the starting hydride-forming alloy is saturated with hydrogen, while the volume of the MH bed remains constant. The last assumption is a limiting estimation because it provides the maximum possible reduction in the porosity during H2 absorption process.The model was validated using published experimental data on a cylindrical MH reactor filled with 422 g of LaNi5. It was shown that accounting the realistic changes in the MH density can significantly affect the simulation results.

Engaging Alkenes in Metallaphotoredox: A Triple Catalytic, Radical Sorting Approach to Olefin-Alcohol Cross-Coupling.

Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via single-electron reactivity. Correspondingly, expanding metallaphotoredox to encompass new C(sp3)-coupling partners could provide entry to a novel, medicinally relevant chemical space. In particular, alkenes are abundant, bench-stable, and capable of versatile C(sp3)-radical reactivity via metal-hydride hydrogen atom transfer (MHAT), although metallaphotoredox methodologies invoking this strategy remain underdeveloped. Importantly, merging MHAT activation with metallaphotoredox could enable the cross-coupling of olefins with feedstock partners such as alcohols, which undergo facile open-shell activation via photocatalysis. Herein, we report the first C(sp3)-C(sp3) coupling of MHAT-activated alkenes with alcohols by performing deoxygenative hydroalkylation via triple cocatalysis. Through synergistic Ir photoredox, Mn MHAT, and Ni radical sorting pathways, this branch-selective protocol pairs diverse olefins and methanol or primary alcohols with remarkable functional group tolerance to enable the rapid construction of complex aliphatic frameworks.