Thermodynamics and kinetics of hydriding and dehydriding reactions in Mg-based hydrogen storage materials

Mg-based materials are one of the most promising hydrogen storage candidates due to their high hydrogen storage capacity,environmental benignity,and high Clarke number characteristics.However,the limited thermodynamics and kinetic properties pose major challenges for their engineering applications.Herein,we review the recent progress in improving their thermodynamics and kinetics,with an emphasis on the models and the influence of various parameters in the calculated models.Subsequently,the impact of alloying,composite,and nanocrystallization on both thermodynamics and dynamics are discussed in detail.In particular,the correlation between various modification strategies and the hydrogen capacity,dehydrogenation enthalpy and temperature,hydriding/dehydriding rates are summarized.In addition,the mechanism of hydrogen storage processes of Mg-based materials is discussed from the aspect of classical kinetic theories and microscope hydrogen transferring behavior.This review concludes with an outlook on the remaining challenge issues and prospects.

Improved hydrogen storage kinetics of MgH_(2) using TiFe_(0.92)Mn_(0.04)Co_(0.04) with in-situ generated α-Fe as catalyst

While TiFe alloy has recently attracted attention as the efficient catalyst to enhance de/hydrogenation rates of Mg/MgH_(2),the difficulty of its activation characteristics has hindered further improvement of reaction kinetics.Herein,we report that the TiFe_(0.92)Mn_(0.04)Co_(0.04) catalyst can overcome the abovementioned challenges.The synthesized MgH_(2)-30 wt% TiFe_(0.92)Mn_(0.04)Co_(0.04) can release 4.5 wt%of hydrogen in 16 min at 250℃,three times as fast as MgH_(2).The activation energy of dehydrogenation was as low as 84.6 kJ mol^(-1),which is 46.8%reduced from pure MgH_(2).No clear degradation of reaction rates and hydrogen storage capacity was observed for at least 30 cycles.Structural studies reveal that TiFe_(0.92)Mn_(0.04)Co_(0.04) partially decomposes to in-situ generatedα-Fe particles dispersed on TiFe_(0.92)Mn_(0.04)Co_(0.04).The presence ofα-Fe reduces the formation of an oxide layer on TiFe_(0.92)Mn_(0.04)Co_(0.04),enabling the activation processes.At the same time,the hydrogen incorporation capabilities of TiFe_(0.92)Mn_(0.04)Co_(0.04) can provide more hydrogen diffusion paths,which promote hydrogen dissociation and diffusion.These discoveries demonstrate the advanced nature and importance of combining the in-situ generatedα-Fe with TiFe_(0.92)Mn_(0.04)Co_(0.04).It provides a new strategy for designing highly efficient and stable catalysts for Mg-based hydrogen storage materials.

Kinetics in Mg-based hydrogen storage materials:Enhancement and mechanism

Mg-based materials have been intensively studied for hydrogen storage applications due to their high energy density up to 2600 Wh/kg or 3700 Wh/L.However,the Mg-based materials with poor kinetics and the necessity for a high temperature to achieve 0.1 MPa hydrogen equilibrium pressure limit the applications in the onboard storage in Fuel cell vehicles(FCVs).Over the past decades,many methods have been applied to improve the hydriding/dehydriding(H/D)kinetics of Mg/MgH 2 by forming amorphous or nanosized particles,adding catalysts and employing external energy field,etc.However,which method is more effective and the intrinsic mechanism they work are widely differing versions.The hydrogenation and dehydrogenation behaviors of Mg-based alloys analyzing by kinetic models is an efficient way to reveal the H/D kinetic mechanism.However,some recently proposed models with physical meaning and simple analysis method are not known intimately by researchers.Therefore,this review focuses on the enhancement method of kinetics in Mg-based hydrogen storage materials and introduces the new kinetic models.

Nanostructuring of Mg-Based Hydrogen Storage Materials:Recent Advances for Promoting Key Applications

With the depletion of fossil fuels and global warming,there is an urgent demand to seek green,low-cost,and high-efficiency energy resources.Hydrogen has been considered as a potential candidate to replace fossil fuels,due to its high gravimetric energy density(142 MJ kg^(-1)),high abundance(H_(2)O),and environmentalfriendliness.However,due to its low volume density,effective and safe hydrogen storage techniques are now becoming the bottleneck for the"hydrogen economy".Under such a circumstance,Mg-based hydrogen storage materials garnered tremendous interests due to their high hydrogen storage capacity(~7.6 wt%for MgH_(2)),low cost,and excellent reversibility.However,the high thermodynamic stability(ΔH=-74.7 kJ mol^(-1)H_(2))and sluggish kinetics result in a relatively high desorption temperature(>300℃),which severely restricts widespread applications of MgH_(2).Nano-structuring has been proven to be an effective strategy that can simultaneously enhance the ab/de-sorption thermodynamic and kinetic properties of MgH_(2),possibly meeting the demand for rapid hydrogen desorption,economic viability,and effective thermal management in practical applications.Herein,the fundamental theories,recent advances,and practical applications of the nanostructured Mg-based hydrogen storage materials are discussed.The synthetic strategies are classified into four categories:free-standing nano-sized Mg/MgH_(2)through electrochemical/vapor-transport/ultrasonic methods,nanostructured Mg-based composites via mechanical milling methods,construction of core-shell nano-structured Mg-based composites by chemical reduction approaches,and multi-dimensional nano-sized Mg-based heterostructure by nanoconfinement strategy.Through applying these strategies,near room temperature ab/de-sorption(<100℃)with considerable high capacity(>6 wt%)has been achieved in nano Mg/MgH_(2)systems.Some perspectives on the future research and development of nanostructured hydrogen storage materials are also provided.

Progress in improving thermodynamics and kinetics of new hydrogen storage materials

Hydrogen storage material has been much developed recently because of its potential for proton exchange membrane （PEM） fuel cell applications. A successful solid-state reversible storage material should meet the requirements of high storage capacity, suitable thermodynamic properties, and fast adsorption and desorption kinetics. Complex hydrides, including boron hydride and alanate, ammonia borane, metal organic frameworks （MOFs）, covalent organic frameworks （COFs） and zeolitic imidazolate frameworks （ZIFs）, are remarkable hydrogen storage materials because of their advantages of high energy density and safety. This feature article focuses mainly on the thermodynamics and kinetics of these hydrogen storage materials in the past few years.

INFLUENCE OF TEMPERATURE AND PRESSURE ON THE KINETICS OF Mg-6mol%LaNi PREPARED BY HYDRIDING COMBUSTION SYNTHESIS

A new model to study the hydriding/dehydriding （H/D） kinetic mechanism has been applied in the two-phase （α-β） region of the Mg-6mol%LaNi composite at temperature and pressure ranging from 523 to 623K and 0.256 to 0.992MPa H2. respectively. The coincidence of the theoretical calculation with the experimental data indicates that the rate-limiting step is hydrogen diffusion in the β phase for hydriding process and the diffusion of hydrogen in the α solid solution for hydrogen desorption with activation energies 89500 and 87900J/mol H2 for HID processes, respectively, which were much smaller than those of MgH2 and can be attributed to the La and Ni additions.

Impact of severe plastic deformation on kinetics and thermodynamics of hydrogen storage in magnesium and its alloys

Magnesium and its alloys are the most investigated materials for solid-state hydrogen storage in the form of metal hydrides,but there are still unresolved problems with the kinetics and thermodynamics of hydrogenation and dehydrogenation of this group of materials.Severe plastic deformation(SPD)methods,such as equal-channel angular pressing(ECAP),high-pressure torsion(HPT),intensive rolling,and fast forging,have been widely used to enhance the activation,air resistance,and hydrogenation/dehydrogenation kinetics of Mg-based hydrogen storage materials by introducing ultrafine/nanoscale grains and crystal lattice defects.These severely deformed materials,particularly in the presence of alloying additives or second-phase nanoparticles,can show not only fast hydrogen absorption/desorption kinetics but also good cycling stability.It was shown that some materials that are apparently inert to hydrogen can absorb hydrogen after SPD processing.Moreover,the SPD methods were effectively used for hydrogen binding-energy engineering and synthesizing new magnesium alloys with low thermodynamic stability for reversible low/room-temperature hydrogen storage,such as nanoglasses,high-entropy alloys,and metastable phases including the high-pressureγ-MgH2 polymorph.This work reviews recent advances in the development of Mg-based hydrogen storage materials by SPD processing and discusses their potential in future applications.

Mg-based materials for hydrogen storage

Over the last decade’s magnesium and magnesium based compounds have been intensively investigated as potential hydrogen storage as well as thermal energy storage materials due to their abundance and availability as well as their extraordinary high gravimetric and volumetric storage densities.This review work provides a broad overview of the most appealing systems and of their hydrogenation/dehydrogenation properties.Special emphasis is placed on reviewing the efforts made by the scientific community in improving the material’s thermodynamic and kinetic properties while maintaining a high hydrogen storage capacity.

Effect of ternary transition metal sulfide FeNi_(2)S_(4)on hydrogen storage performance of MgH_(2)

Hydrogen storage is a key link in hydrogen economy,where solid-state hydrogen storage is considered as the most promising approach because it can meet the requirement of high density and safety.Thereinto,magnesium-based materials(MgH_(2))are currently deemed as an attractive candidate due to the potentially high hydrogen storage density(7.6 wt%),however,the stable thermodynamics and slow kinetics limit the practical application.In this study,we design a ternary transition metal sulfide FeNi_(2)S_(4)with a hollow balloon structure as a catalyst of MgH_(2)to address the above issues by constructing a MgH_(2)/Mg_(2)NiH_(4)-MgS/Fe system.Notably,the dehydrogenation/hydrogenation of MgH_(2)has been significantly improved due to the synergistic catalysis of active species of Mg_(2)Ni/Mg_(2)NiH_(4),MgS and Fe originated from the MgH_(2)-FeNi_(2)S_(4)composite.The hydrogen absorption capacity of the MgH_(2)-FeNi_(2)S_(4)composite reaches to 4.02 wt%at 373 K for 1 h,a sharp contrast to the milled-MgH_(2)(0.67 wt%).In terms of dehydrogenation process,the initial dehydrogenation temperature of the composite is 80 K lower than that of the milled-MgH_(2),and the dehydrogenation activation energy decreases by 95.7 kJ·mol-1 compared with the milled-MgH_(2)(161.2 kJ·mol^(-1)).This method provides a new strategy for improving the dehydrogenation/hydrogenation performance of the MgH_(2)material.

Hydrogen sorption properties of nanocrystalline Mg_2FeH_6-based complex and catalytic effect of TiO_2

The diversities of hydrogen sorption properties of Mg2FeH6-based complexes with and without TiO2 were investigated. Mg2FeH6-based complexes with and without TiO2 were synthesized respectively by reactive mechanical alloying,and hydrogen sorption properties of the complexes were examined by Sieverts-type apparatus. The results show that the sample without TiO2 releases 4.43 % (mass fraction) hydrogen in 1.5 ks at 653 K under 0.1 MPa H2 pressure and absorbs 90% of the total 4.43 % (mass fraction) hydrogen absorbed in 85 s at 623 K under 4.0 MPa H2 pressure. But for the sample with TiO2 addition under the same condition,it only needs 400 s to release all of the stored hydrogen and 60 s to absorb 90% of the total hydrogen absorbed. The activation energies for desorption process of the samples with and without TiO2 are determined to be 71.2 and 80.3 kJ/(mol.K),respectively. The improvement in hydrogen sorption rate and and reduction in activation energy can be attributed to the addition of TiO2.

Synthesis of nanostructured Mg_2FeH_6 hydride and hydrogen sorption properties of complex

Reactive mechanical alloying(RMA)was carried out in a planetary ball mill for the synthesis of ternary hydride Mg2FeH6 for hydrogen storage.The formation mechanism of Mg2FeH6 in RMA process and the sorption properties of the products were investigated.The results show that Mg2FeH6 has a yield ratio around 80%,and a grain size below 10 nm in the powder synthesized by milling 3Mg+Fe mixture for 150 h under the hydrogen pressure of 1 MPa.The synthesized powder possesses a high hydrogen capacity and good sorption kinetics,and absorbs 4.42%(mass fraction)of hydrogen within 200 s at 623 K under the hydrogen pressure of 4.0 MPa.In releasing hydrogen at 653 K under 0.1 MPa,it desorbs 4.43%(mass fraction)of hydrogen within 2 000 s.The addition of Ti increases the hydrogen desorption rate of the complex in the initial 120 s of the desorption process.

碳材料在镁基固态储氢领域中的应用进展

镁基储氢材料因其理论储氢密度高(MgH_(2),7.6%(质量分数))、来源广、成本低的特点,被认为是最具应用前景的固态储氢材料之一。但MgH_(2)的放氢焓值高(75 kJ/mol)、放氢温度高(>380℃),造成其动力学和热力学性能差,限制了在固态储氢领域的应用和发展。近年来,碳材料因结构多样化、可调控性强、比表面积大、力学性能高和电子传输能力强等优势,在镁基储氢材料的掺杂改性、纳米限域等方面应用广泛,可以有效改善吸放氢温度、循环性能和吸放氢活化能等性能指标,并取得了大量成果。本文主要针对碳材料在镁基储氢材料中的研究现状,归纳了碳材料的合成和改性方法,重点阐述了不同维度碳材料在镁基储氢领域的应用进展,并展望了未来的发展方向。

Exceptional catalytic effect of novel rGO-supported Ni-Nb nanocomposite on the hydrogen storage properties of MgH_(2)

The design of an excellent active catalyst to improve the sluggish kinetic and thermodynamic properties of magnesium hydride(MgH_(2))remains a great challenge to achieve its practical application.In this study,a novel Ni-Nb/rGO nanocomposite catalyst was successfully prepared by one-spot hydrothermal and sub-sequent calcination methods.The novel Ni-Nb/rGO nanocomposite exhibits an exceptional catalytic effect on improving MgH_(2) sorption properties.Specifically,the onset desorption temperature of MgH_(2)+10 wt%Ni-Nb/rGO composite is reduced to 198℃,much lower than that of undoped MgH_(2)(330℃).In-terestingly,the composite can release 5.0,5.9,and 6.0 wt%H_(2) within 10 min at 245,260,and 275℃,respectively.Furthermore,the dehydrogenated MgH_(2)+10 wt%Ni-Nb/rGO composite starts to absorb hydrogen even at room temperature with approximate 2.75 wt%H_(2) uptake at 75℃under 3 MPa H_(2) pressure within 30 min and exhibits excellent stability by maintaining 6.0 wt%hydrogen content after 20 cycles at 300℃.Chou’s model suggests that the de/hydrogenation kinetics of Ni-Nb/rGO-modified MgH_(2) switches from surface penetration model to diffusion model at lower temperatures.Additionally,the ac-tivation energies(E a)for the de/hydrogenation of MgH_(2)+10 wt%Ni-Nb/rGO are reduced to 57.8 kJ/mol and 33.9 kJ/mol,which are significantly lower than those of undoped MgH_(2).The work demonstrates that the addition of a novel ternary Ni-Nb/rGO catalyst is an effective strategy to not only boost the sorption kinetics of MgH_(2) but also maintain its cycling property.

Li-Mg-N-H体系储氢材料的研究进展

在固态储氢材料中,Li-Mg-N-H体系储氢材料因其热力学性能好、可逆性好、理论储氢容量高等特点被认为是最有前景的储氢材料。然而,由于Li-Mg-N-H体系的动力学性能较差,导致其在200℃以上才能进行快速吸放氢反应。因此,文章从成分调控、纳米化和掺杂催化剂3个方面论述了Li-Mg-N-H体系热力学和动力学调控的研究现状,并指出未来研究方向。

Effect of Ball Milling Time on Microstructure and Hydrogen Storage Properties of Nd_(5)Mg_(41)Ni Alloy

Mg-based alloys must be dehydrogenated at high pressure and temperatures, limiting their practical application. In this paper, Nd_(5)Mg_(41)Ni alloy was prepared by vacuum melting, and the as-cast alloy was ball milled for 5 h, 10 h, 15 h, and 20 h. The effect of ball milling time on the microstructure and hydrogen storage properties of the alloy was systematically studied. The alloy comprises Nd_(5)Mg_(41), NdMg_(12), NdMg_(3), and Mg_(2)Ni phases. The Nd_(5)Mg_(41)Ni alloy milling for 10 h can reach 95% of the saturated hydrogen absorption at 553 K by 40 s, and the alloy can desorb hydrogen only by 20 min. The dehydrogenation activation energy is only 99.9 kJ/mol H_(2). Ball milling makes the alloy produce many nanocrystalline and amorphous structures. The nano-grain boundary provides a channel for the diffusion of hydrogen atoms, and the high energy at the grain boundary provides energy for the phase deformation nucleus. Ball milling leads to the refinement of alloy particles and shortens the diffusion distance of hydrogen atoms to the interior of alloy particles. Defects such as twins and dislocations generated by milling provide energy for the phase deformation nucleus during the hydrogen absorption and desorption.

Studies on a New Material for Hydrogen Storage and Supply by Modified Fe and Fe2O3 Powder

Modified iron oxide, a new material for hydrogen storage and supply to polymer electrolyte fuel cell （PEFC）, was prepared by impregnating Fe or Fe2O3 powder with an aqueous solution containing metal cation additives （Al, Cr, Ni, Co, Zr and Mo）. Hydrogen storage properties of the samples were investigated. The results show that both Fe and Fe2O3 powder with additive Mo presented excellent catalytic activity and cyclic stability, and their hydrogen producing temperature could be surprisingly decreased. The temperature of forming hydrogen for the Fe2O3-Mo at the rate of 250 μmol·min^-1·Fe-g^-1 could be dramatically decreased from 527 ℃ before addition of Mo to 283 ℃ after addition of Mo in the fourth cycle. The cause for it was probably related to preventing the sinter of the sample particles. In addition, hydrogen storage capacity of the Fe2O3-Mo can reach w=4.5% （72 kg H2/m^3）, close to International Energy Agency （IEA） criterion. These show the value of practical application of the Fe2O3-Mo as the promising hydrogen storage material.

Microstructure and hydrogen storage properties of Mg-based Mg85Zn5Ni10 alloy powders

Mg85Zn5Ni10 ternary alloy was synthesized through vacuum induction melting for the first time.Phase compositions and microstructures of Mg85Zn5Ni10 alloy powders were analyzed by X-ray diffraction (XRD)and scanning electron micro- scopy (SEM).By utilizing a Sieverts apparatus,the hydrogenation and dehydrogenation properties of Mg85Zn5Ni10 powders were measured systematically.XRD and SEM results indicated that the Mg85Zn5Ni10 alloy powders contained the major phase Mg,the eutectic Mg-Mg2Ni and Mg-MgZn2 mixtures.The possible reaction pathway can be inferred as follows:Mg +Mg2Ni +MgZn2 +H2←→MgH2+Mg2NiH4 +MgZn2,indicating that MgZn2 did not react with H2. After activation,the Mg85Zn5Ni10 alloy powders could absorb 5.4 wt.% hydrogen reversibly and held an excellent hydrogenation kinetics at a relatively low temperature.At 360 ℃,the alloy powders desorbed 5.351 wt.% hydrogen in 264 s.However,it only had fast dehydrogenation kinetics above 300 ℃.The existence of MgZn2 contributed to improving the kinetic properties.During the hydriding and dehydriding,the formed cracks and defects promoted the kinetics and thermodynamic properties.The activation energy for dehydrogenation was 75.514 kJ/mol.The enthalpy change values of hydrogenation and dehydrogenation were calculated to be -73.064 kJ/mol and 76.674 kJ/mol,respectively,indicating that melting with Ni and Zn could improve the thermodynamic property of Mg slightly.

储氢材料性能测试装置设计及应用

通过对储氢材料储氢过程特点的分析 ,自行设计安装了一套测量储氢材料储氢性能的装置。利用该装置在恒容条件测试具有不同初始氢气压力的吸氢动力学曲线 ,以双排水法测试放氢动力学曲线 ,并可通过合适的步骤 ,测得储氢材料的PCT曲线。用该装置对机械球磨获得的镁基储氢材料 (Mg Ni MnO2 )进行储氢性能测试。结果表明 :该测试装置设计合理 ,测试过程可靠 ;由机械球磨获得的镁基储氢材料的吸放氢动力学性能优异 ,其PCT曲线表明其吸放氢的滞后性小 ,在吸放氢循环过程中能量损失小。

Influence of TiC catalyst on absorption/desorption behaviors and microstructures of sodium aluminum hydride

TiC-doped NaA1H4 complex hydrides were prepared by hydrogenation of ball-milled Nail/A1 mixture with x TiC powder （x = 0, 5%, 8%, 10%, mole fraction）. The effects of TiC catalyst content on the absorption/desorption behaviors of the samples were investigated. The results show that TiC can improve the hydriding/dehydriding kinetics of sodium aluminum hydride, the hydriding rate of the sample increases with increasing TiC content. It is found that the TiC-doped NaA1H4 composites have a relatively good cyclic stability. The composite doped with 10% TiC maintains steadily about 4.5% （mass fraction） hydrogen absorption capacity as against about 3.8% （mass fraction） hydrogen desorption capacity over 8 cycles. The particle sizes of the TiC-doped NaA1H4 composites can be reduced to 50-100 nm, which may play an important role in improving the hydriding/dehydriding kinetics.

纳米储氢材料在推进剂中的应用研究进展

储氢材料的放氢热力学和动力学特性是影响其在固体推进剂中应用效果的重要因素,纳米化可以有效调节不同种类储氢材料的放氢热力学和动力学特性。综述指出纳米化学吸附储氢材料具有更低的放氢温度和更快的放氢速率,有利于在推进剂燃烧过程中充分利用储氢材料中所含的氢;纳米化学-物理吸附储氢材料可同时作为推进剂的氢源和燃烧催化剂;对物理吸附储氢材料的纳米结构特征的调节则有希望使其具备常温下能快速吸放氢的能力,有较好的应用前景。纳米储氢材料在固体推进剂中应用的关键在于掌握推进剂对储氢材料热力学和动力学特性的要求,从而依据要求通过纳米化手段对其进行调节,以获得具备适宜热力学和动力学特性的储氢材料。