Recent advances on surface metal hydrides studied by solid-state nuclear magnetic resonance spectroscopy

Metal hydrides (MeH) on solid surfaces, i.e., surface MeH, are ubiquitous but criticalspecies in heterogeneous catalysis, and their intermediate roles have been proposed innumerous reactions such as (de)hydrogenation and alkanes activation, etc., however, thedetailed spectroscopic characterizations remain challenging. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy has become a powerful tool in surface studies, asit provides access to local structural characterizations at atomic level from multipleviews, with comprehensive information on chemical bonding and spatial structures. Inthis review, we summarized and discussed the latest research developments on thesuccessful application of ssNMR to characterize surface MeH species on solid catalystsincluding supported single-site heterogeneous catalysts, bulk metal oxides and metalmodified zeolites. We also discussed the opportunities and challenges in this field, aswell as the potential application/development of state-of-the-art ssNMR technologies toenable further exploration of metal hydrides in heterogeneous catalysis.

Degradation Behavior of Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

The degradation mechanism of electrochemical performance of sealed type nickel/metal hydride batteries was investigated. The results indicate that the degradation behavior of Ni/MH battery is not only owing to the lack of electrolyte, but also the deterioration of the active materials on the positive and negative electrodes of Ni/MH batteries. Scanning electron micrographs (SEM), X ray diffraction (XRD) and laser granularity analyses are presented. The particle pulverization and oxidation during charge/discharge are identified as the main causes for deterioration of the negative and positive electrode in nickel/metal hydride batteries, as well as the cross section cracking of both anode and cathode.

The electrochemical characteristics of AB_(4)-type rare earth-Mg-Ni-based superlattice structure hydrogen storage alloys for nickel metal hydride battery

Rare earth-Mg-Ni-based alloys with superlattice structures are new generation negative electrode materials for the nickel metal hydride batteries.Among them,the novel AB_(4)-type superlattice structure alloy is supposed to have superior cycling stability and rate capability.Yet its preparation is hindered by the crucial requirement of temperature and the special composition which is close to the other superlattice structure.Here,we prepare rare earth-Mg-Ni-based alloy and study the phase transformation of alloys to make clear the formation of AB_(4)-type phase.It is found Pr_(5)Co_(19)-type phase is converted from Ce_(5)Co_(19)-type phase and shows good stability at higher temperature compared to the Ce_(5)Co_(19)-type phase in the range of 930-970℃.Afterwards,with further 5℃increasing,AB_(4)-type superlattice structure forms at a temperature of 975℃by consuming Pr_(5)Co_(19)-type phase.In contrast with A_(5)B_(19)-type alloy,AB_(4)-type alloy has superior rate capability owing to the dominant advantages of charge transfer and hydrogen diffusion.Besides,AB_(4)-type alloy shows long lifespan whose capacity retention rates are 89.2%at the 100;cycle and 82.8%at the 200;cycle,respectively.AB_(4)-type alloy delivers 1.53 wt.%hydrogen storage capacity at room temperature and exhibits higher plateau pressure than Pr_(5)Co_(19)-type alloy.The work provides novel AB_(4)-type alloy with preferable electrochemical performance as negative electrode material to inspire the development of nickel metal hydride batteries.

Preparation and Electrochemical Performances of Nickel Metal Hydride Batteries with High Specific Volume Capacity

Cylindrical nickel metal hydride （Ni-MH） battery with high specific volume capacity was prepared by using the oxyhydroxide Ni（OH）2 and AB5 type hydrogen storage alloy and adjusting the designing parameters of positive and negative electrodes. The oxyhydroxide Ni（OH）2 was synthesized by oxidizing spherical β-Ni（OH）2 with chemical method. The X-ray diffraction （XRD） patterns and the Fourier transform infrared （PT-IR） spectra indicated that 7-NiOOH was formed on the oxyhydroxide Ni（OH）2 powders, and some H2O molecules were inserted into their crystal lattice spacing. The battery capacity could not be improved when the oxyhydroxide Ni（OH）2 sample was directly used as the positive active materials. However, based on the conductance and residual capacity of the oxyhydroxide Ni（OH）2 powders, AA size Ni-MH battery with 2560 mA.h capacity and 407 W·h·L^-1 specific volume energy at 0.2C was obtained by using the commercial spherical β-Ni（OH）2 and AB5-type hydrogen-storage alloy powders as the active materials when 10% mass amount of the oxyhydroxide Ni（OH）2 with 2.50 valence was added to the positive active materials and subsequently the battery designing parameters were adjusted as well. The as-prepared battery showed 70% initial capacity after 80 cycles at 0.5C. The possibility for adjusting the capacity ratio of positive and negative electrodes from 1 ： 1.35 to 1 ： 1.22 was demonstrated preliminarily. It is considered the as-prepared battery can meet the requirement of some special portable electrical instruments.

Hydrogen storage over alkali metal hydride and alkali metal hydroxide composites

Alkali metal hydroxide and hydride composite systems contain both protic （H bonded with O） and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals, i.e., -23 kJ/molnz for LiOH-LiH, 55.34 kJ/moln： for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150 ℃; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molHz, and the corresponding entropy was ca. 101.23 J/（molHz .K）, so the temperature for releasing 1.0 bar H2 was as high as 518 ℃, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be 57.87 kJ/mol, showing good kinetic properties.

Metal hydride work pair development and its application on automobile air conditioning systems

Aiming at developing exhaust gas driving automobile air conditioning systems, a hydride pair LaNi4.61Mn0.26A10.13/ La0.6Y0.4Ni4.8Mn0.2 was developed working at 393-473 K/293-323 K/263-273 K. Property tests showed that both alloys have flat plateau slopes and small hystereses; system theoretical coefficient of performance （COP） is 0.711. Based on this work pair, a function proving automobile metal hydride refrigeration system was constructed. The equivalent thermal conductivities of the activated reaction beds were merely 1.1-1.6 W/（m-K）, which had not met practical requirement. Intermittent refrigeration cycles were achieved and the average cooling power was 84.6 W at 423 K/303 K/273 K with COP being 0.26. By altering cycling parameters, experiment data showed that cooling power and system COP increase with the growth of heat source temperature as well as pre-heating and regeneration time while decrease with heat sink temperature increment. This study confirms the feasibility of automobile metal hydride refrigeration systems, while heat transfer properties of reaction beds still need to be improved for better performance.

High Purity Hydrogen Production by Metal Hydride System:A Parametric Study Based on the Lumped Parameter Model

The simulation of hydrogen purification in a mixture gas of hydrogen/carbon dioxide (H2/CO2) by metal hydride system was reported.The lumped parameter model was developed and validated.The validated model was implemented on the software Matlab/Simulink to simulate the present investigation.The simulation results demonstrate that the purification efficiency depends on the external pressure and the venting time.An increase in the external pressure and enough venting time makes it possible to effectively remove the impurities from the tank during the venting process and allows to desorb pure hydrogen.The impurities are partially removed from the tank for low external pressure and venting time during the venting process and the desorbed hydrogen is contaminated.Other parameters such as the overall heat transfer coefficient,solid material mass,supply pressure,and the ambient temperature influence the purification system in terms of the hydrogen recovery rate.An increase in the overall heat transfer coefficient,solid material mass,and supply pressure improves the hydrogen recovery rate while a decrease in the ambient temperature enhances the recovery rate.

MICROSTRUCTURE AND ELECTROCHEMICAL CHARACTERISTICS OF Zr_(0.9)Ti_(0.1)(Ni_(1.1)Mn_(0.7)V_(0.2))_x METAL HYDRIDE ELECTRODE

The crystal structure, the phase composition and the electrochemical characteristics of Zr0.9Ti0.1(Ni1.1Mn0.7V0.2)x (x=0.90, 0.95, 1.00, 1.05) alloys were investigated by means of XRD, SEM, EDS and electrochemical measurements. It was shown that all alloys are multiphase with C15 Laves phase as a main phase along with C14 phase and some secondary phases. And the amounts of the C14 phase and secondary phases in the four alloys increases with decreasing x. The results indicated that the various stoichiometric ratios have great effects on the electrochemical characteristics such as the maximum discharge capacity, discharge rate capability and self-discharge properties etc. for Zr0.9Ti0.1(Ni1.1Mn0.7 V0.2)X (x=0.90, 0.95, 1.00, 1.05) alloys. The hyper-stoichiometric Zr0.9 Ti0.1(N1.1Mn0.7 V0.20)1.05 exhibits the maximum discharge capacity of 332mAh-g-1. The C14 phase and secondary phases seems to improve discharge rate capability of the alloys.

Effect of Overcharge on Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

The effects of overcharge on electrochemical performance of AA size sealed-type nickel/metal hydride（Ni/MH） batteries and its degradation mechanism were investigated. The results indicated that the relationship between the effects of different overcharge currents on the increasing velocity of inner pressure and the degradation velocity of cycle life and discharge voltage remains in almost direct proportion. After overcharge cycles, the positive electrode materials remain the original structure, but there occur some breaks because of the irreversible expand of crystal lattice. And the negative electrode alloy particles have inconspicuous pulverization, but are covered with lots of corrosive products and its main component is rare earth hydroxide or oxide. These are all the main reasons leading to the degradation behavior of the discharge capacity and cycle life of Ni/MH batteries.

High-performance nickel metal hydride battery anode with enhanced durability and excellent low-temperature discharge capability

Current AB_(5)-type hydrogen storage alloys employed in nickel-metal hydride(NiMH)batteries exhibit exceptional low-temperature discharge performance but suffer from limited cycle life and insufficient high-temperature stability.To overcome these challenges,we introduce a hydrothermal synthesized LaF_(3)coating layer on the surface of the AB_(5)anode material.This LaF_(3)coating layer adds a protective barrier for the active material,significantly improving the battery's cycle life and high-temperature stability.Our findings indicate that(1)the LaF_(3)coated anode demonstrates an extended cycle life with increased specific capacity and a capacity retention of 88%after 40 cycles of abusive overcharging and rapid discharging at room temperature.(2)The synthesized anode exhibits a 97%recovery of its specific capacity of 292.7 mAh/g following 144 h of high-temperature storage.(3)The low-temperature discharge capacity of the synthesized anode remains on par with the pristine AB_(5)alloy at 230.4 mAh/g in a-40℃environment.This research presents a significant advancement in hydrogen storage alloy coatings and offers valuable insights for designing electrodes in NiMH batteries.

The Coupling of Synthesis and Electrochemistry to Enable the Reversible Storage of Hydrogen as Metal Hydrides

Given its high gravimetric energy density and status as a clean fuel when derived from renewables,hydrogen(H2)is considered a premier candidate for energy storage;however,its low volumetric density limits its broader application.Chemical storage through the reversible incorporation of H2 into chemical bonds offers a promising solution to its low volumetric density,circumventing subpar energy densities and substantial infrastructure investments associated with physical storage methods.Metal hydrides are promising candidates for chemical storage because of their high gravimetric capacity and tunability through nanostructuring and alloying.Moreover,metal hydride/H2 interconversion may be interfaced with electrochemistry,which offers potential solutions to some of the challenges associated with traditional thermochemical platforms.In this Perspective,we describe anticipated challenges associated with electrochemically mediated metal hydride/H2 interconversion,including thermodynamic efficiencies of metal hydride formation,sluggish kinetics,and electrode passivation.Additionally,we propose potential solutions to these problems through the design of molecular mediators that may control factors such as metal hydride solubility,particle morphology,and hydride affinity.Realization of an electrochemically mediated metal hydride/H2 interconversion platform introduces new tools to address challenges associated with hydrogen storage platforms and contributes toward the development of room-temperature hydrogen storage platforms.

Thermal performance of a metal hydride reactor for hydrogen storage with cooling/heating by natural convection

Metal hydride(MH)systems can be used for storage in stationary facilities of hydrogen with a high volume density at temperatures and pressures close to ambient ones.Recently,the possibility of using passive heating/cooling systems or regenerative heat exchangers has been studied to improve the energy efficiency of MH systems for hydrogen storage without the need for forced circulation of a heating/cooling fluid.Natural convection of air may be used to passively remove/add heat as required for proper operation of a MH reactor.Under these conditions,the MH reactor can operate at a constant ambient air temperature and be driven by a difference in pressure between the source and the consumer of hydrogen.Since operation of MH systems with natural convective heating/cooling has not been systematically investigated as yet,a tubular MH reactor based on this principle is examined in this paper.Two-thirds of the internal volume ofø25.4×1 mm tube is occupied by a composition of LaNi5 and aluminium foam(one linear metre contains 1.1 kg of LaNi5 with a hydrogen capacity of 153 NL H2).Annular fins are used to increase heat transfer to air.Detailed and simplified mathematical models of the systems of this class are proposed and validated.It is shown that acceptable hydrogen charging/discharging rates in such systems are achieved with proper selection of fining characteristics.Charging from a hydrogen source at a pressure of 10 atm and an ambient air temperature of 10 to 30℃ takes 15 min.A reactor with a length of 1 m can desorb almost all stored hydrogen at a minimum outlet pressure of 0.45 bar to feed 30-300 W fuel cells.

The development of metal hydrides using as concentrating solar thermal storage materials

Metal hydrides high temperature thermal heat storage technique has great promising future prospects in solar power generation, industrial waste heat utilization and peak load regulating of power system. This article introduces basic principle of metal hydrides for thermal storage, and summarizes developments in advanced metal hydrides high-temperature thermal storage materials, numerical simulation and thermodynamic calculation in thermal storage systems, and metal hydrides thermal storage prototypes. Finally, the future metal hydrides high temperature thermal heat storage technique is been looked ahead.

Mathematical Modeling of Pneumatic Artificial Muscle Actuation via Hydrogen Driving Metal Hydride-LaNi5

Quantitative understanding of mechanical actuation of intricate Pneumatic Artificial Muscle （PAM） actuators is technically required in control system design for effective real-time implementation. This paper presents mathematical modeling of the PAM driven by hydrogen-gas pressure due to absorption and desorption of metal hydride. Empirical models of both mechanical actuation of industrial PAM and chemical reaction of the metal hydride-LaNi5 are derived systematically where their interac- tions comply with the continuity principle and energy balance in describing actual dynamic behaviors of the PAM actuator （PAM and hydriding/dehydriding-reaction bed）. Simulation studies of mechanical actuation under various loads are conducted so as to present dynamic responses of the PAM actuators. From the promising results, it is intriguing that the heat input for the PAM actuator can be supplied to, or pumped from the reaction bed, in such a way that absorption and desorption of hydrogen gas take place, respectively, in controlling the pressure of hydrogen gas within the PAM actuator. Accordingly, this manipulation results in desired mechanical actuation of the PAM actuator in practical uses.

Research on MetalHydride Compressor System

TiZr series Laves phase hydrogen storage alloys with good hydrogen storage properties, such as large hydrogen capacity, rapid hydriding and dehydriding rate, high compression ratio, gentle plateau, small hysteresis, easily being activated and long cyclic stability etc. for metal hydride compressor have been investigated. In addition, a hydride compressor with special characteristics, namely, advanced filling method, good heat transfer effect and reasonable structural design etc. has also been constructed. A hydride compressor cryogenic system has been assembled coupling the compressor with a JT microthrottling refrigeration device and its cooling capacity can reach 0.4 W at 25 K.

A 38 MPa Compressor Based on Metal Hydrides

Known as one of the most promising application of metal hydride(MH),the MH compressor can afford hydrogen with high pressure and high purity.Two AB5 type multi-component hydrogen storage alloys and vanadium are studied for the purpose of high pressure compression.A compact compression system has been built.Each designed small-size reactor contains seven special stainless-steel pipes.The single stage compressor can improve the hydrogen pressure from 2 up to 35 MPa with the hydrogen desorbed per unit mass of 207.8 mL/g.The two-stage compression can output hydrogen with pressure of 38 MPa steadily in whole 5.7 mol hydrogen output flow.However,its hydrogen desorbed per unit mass was only computed to 106.9 mL/g as a result of two reactors used in the cycle and the output mass of hydrogen increased less.

Hydrogen recovery from big-scale porous metal hydride(MH)reactor:impact of pressure and MH-thermophysical properties

An advanced ANSYS FLUENT-based model was developed for hydrogen recovery from a multi-tubular fixed-bed metal hydride(MH)reactor of large-scale design.The model was firstly validated by comparing its results to specific experimental data.Mass and heat transfer processes inside the fixed bed were investigated for various pressures and thermochemical characteristics of the MH(thermal conductivity,porosity and reaction parameters).The findings were reported as average,local and spatial changes in the metal’s bed temperature and hydrogen content.During the initial stage of the endothermic desorption(t<100 s),the bed temperature dropped dramat-ically in all cases.During this time,there was a massive emission of hydrogen.The bed temperature was then raised due to the reactor’s external convective heating,while the hydrogen release continued until the MH was completely dehydrided.The dehydrogenation rate of the MH was enhanced when the discharge pressure was raised.Furthermore,some other characteristics of the MH,i.e.,porosity,thermal conductivity,desorption rate constant and activation energy,significantly impacted the resulting mass and heat fluxes inside the bed material.

Some Rare Earth Metallic Organohydrides with Biindenyl as the Ligand

Introduction It is well known that organometallic hydrides of rare earth metals are the catalysts and reducing reagents for the catalysis polymerization of alkenes and the catalysis hydrogenation of alkenoalkynes. There are four methods for the syntheses of organometallic hydrides of rare earth metals:（1） the thermal atomization of metals, i.e., the interaction of a rare earth metal with alkenes with a terminal alkyne;（2） the Ln—Cσ bond is broken with H;;（3） metal-

Growth of a-Plane GaN Films on r-Plane Sapphire by Combining Metal Organic Vapor Phase Epitaxy with the Hydride Vapor Phase Epitaxy

Hydride vapor phase epitaxy （HVPE） is utilized to grow nonpolar a-plane GaN layers on r-plane sapphire templates prepared by metal organic vapor phase epitaxy （MOVPE）. The surface morphology and microstructures of the samples are characterized by atomic force microscopy. The full width at half maximum （FWHM） of the HVPE sample shows a W-shape and that of the MOVPE sample shows an M-shape plane with the degree of 0 in the high-resolution x-ray diffraction （HRXRD） results. The surface morphology attributes to this significant anisotropic. HRXRD reveals that there is a significant reduction in the FWHM, both on-axis and off-axis for HVPE GaN are compared with the MOVPE template. The decrease of the FWHM of E2 （high） Raman scat tering spectra further indicates the improvement of crystal quality after HVPE. By comparing the results of secondary- ion-mass spectroscope and photoluminescence spectrum of the samples grown by HVPE and MOVPE, we propose that C-involved defects are originally responsible for the yellow luminescence.

Development and experimental validation of kinetic models for the hydrogenation/dehydrogenation of Mg/Al based metal waste for energy storage

With the increased use of renewable energy sources,the need to store large amounts of energy will become increasingly important in the near future.A cost efficient possibility is to use the reaction of recycled Mg waste with hydrogen as thermo-chemical energy storage.Owing to the high reaction enthalpy,the moderate pressure and appropriate temperature conditions,the broad abundance and the recyclability,the Mg/Al alloy is perfectly suitable for this purpose.As further development of a previous work,in which the performance of recycled Mg/Al waste was presented,a kinetic model for hydro-and dehydrogenation is derived in this study.Temperature and pressure dependencies are determined,as well as the rate limiting step of the reaction.First experiments are carried out in an autoclave with a scaled-up powder mass,which is also used to validate the model by simulating the geometry with the scaled-up experiments at different conditions.