Improvement effect of reversible solid solutions Mg_(2)Ni(Cu)/Mg_(2)Ni(Cu)H_(4)on hydrogen storage performance of MgH_(2)

The hydrogen absorption/desorption kinetic properties of MgH_(2)can be effectively enhanced by doping specific catalysts.In this work,MOFs-derived NiCu@C nanoparticles(~15 nm)with regular core-shell structure were successfully prepared and introduced into MgH_(2)(denoted as MgH_(2)-NiCu@C).The onset and peak temperatures of hydrogen desorption of MgH_(2)-11 wt.%NiCu@C are 175.0℃and282.2℃,respectively.The apparent activation energy of dehydrogenated reaction is 77.2±4.5 kJ/mol for MgH_(2)-11 wt.%NiCu@C,which is lower than half of that of the as-milled MgH_(2).Moreover,MgH_(2)-11 wt.%NiCu@C displays great cyclic stability.The strengthening"hydrogen pumping"effect of reversible solid solutions Mg_(2)Ni(Cu)/Mg_(2)Ni(Cu)H_(4)is proposed to explain the remarkable improvement in hydrogen absorption/desorption kinetic properties of MgH_(2).This work offers a novel perspective for the design of bimetallic nanoparticles and beyond for application in hydrogen storage and other energy related fields.

Effects of highly dispersed Ni nanoparticles on the hydrogen storage performance of MgH_(2)

MgH_(2)with a large hydrogen capacity is regarded as a promising hydrogen storage material.However,it still suffers from high thermal stability and sluggish kinetics.In this paper,highly dispersed nano-Ni has been successfully prepared by using the polyol reduction method with an average size of 2.14 nm,which significantly improves the de/rehydrogenation properties of MgH_(2).The MgH_(2)–10wt%nano-Ni sample starts releasing H_(2)at 497 K,and roughly 6.2wt%H_(2)has been liberated at 583 K.The rehydrogenation kinetics of the sample are also greatly improved,and the adsorption capacity reaches 5.3wt%H_(2)in 1000 s at 482 K and under 3 MPa hydrogen pressure.Moreover,the activation energies of de/rehydrogenation of the MgH_(2)–10wt%nano-Ni sample are reduced to(88±2)and(87±1)kJ·mol−1,respectively.In addition,the thermal stability of the MgH_(2)–10wt%nano-Ni system is reduced by 5.5 kJ per mol H_(2)from that of pristine MgH_(2).This finding indicates that nano-Ni significantly improves both the thermodynamic and kinetic performances of the de/rehydrogenation of MgH_(2),serving as a bi-functional additive of both reagent and catalyst.

Hydrogen storage performances of as-milled REMg_(11)Ni(RE=Y, Sm) alloys catalyzed by MoS_2

To compare the hydrogen storage performances of as-milled REMg11Ni-5MoS2(mass fraction)(RE=Y,Sm)alloys,which were catalyzed by MoS2,the corresponding alloys were prepared.The hydrogen storage performaces of these alloys were measured by various methods,such as XRD,TEM,automatic Sievert apparatus,TG and DSC.The results reveal that both of the as-milled alloys exhibit a nanocrystalline and amorphous structure.The RE=Y alloy shows a larger hydrogen absorption capacity,faster hydriding rate,lower initial hydrogen desorption temperature,superior hydrogen desorption property,and lower hydrogen desorption activation energy,which is thought to be the reason of its better hydrogen storage kinetics,as compared with RE=Sm alloy.

Enhancing hydrogen storage performance via optimizing Y and Ni element in magnesium alloy

Magnesium-based hydrogen storage materials are considered as one of the most promising candidates for solid state hydrogen storage due to their advantages of high hydrogen capacity,excellent reversibility and low cost.In this paper,Mg_(91.4)Ni_(7)Y_(1.6) and Mg_(92.8)Ni_(2.4)Y_(4.8) alloys were prepared by melting and ball milling.Their microstructures and phases were characterized by X-ray diffraction,scanning electron microscope and transmission electron microscope,and hydrogen absorbing and desorbing properties were tested by the high pressure gas adsorption apparatus and differential scanning calorimetry(DSC).In order to estimate the activation energy and growth mechanism of alloy hydride,the JMAK,Arrhenius and Kissinger methods were applied for calculation.The hydrogen absorption content of Mg_(92.8)Ni_(2.4)Y_(4.8) alloy reaches 3.84 wt.%within 5 min under 350℃,3 MPa,and the maximum hydrogen capacity of the alloy is 4.89 wt.%in same condition.However,the hydrogen absorption of Mg_(91.4)Ni_(7)Y_(1.6) alloy reaches 5.78 wt.%within 5 min,and the maximum hydrogen absorption of the alloy is 6.44 wt.%at 350℃and 3 MPa.The hydrogenation activation energy of Mg_(94.4)Ni_(7)Y_(1.6) alloy is 25.4 kJ/mol H_(2),and the enthalpy and entropy of hydrogen absorption are-60.6 kJ/mol H_(2) and 105.5 J/K/mol H_(2),separately.The alloy begins to dehydrogenate at 210℃,with the dehydrogenation activation energy of 87.7 kJ/mol H_(2).By altering the addition amount of Ni and Y elements,the 14 H-LPSO phase with smaller size and ternary eutectic areas with high volume fraction are obtained,which provides more phase boundaries and catalysts with better dispersion,and there are a lot of fine particles in the alloy,these structures are beneficial to enhance the hydrogen storage performance of the alloys.

Magnesium nickel hydride monocrystalline nanoparticles for reversible hydrogen storage

Although Mg-based hydrides are extensively considered as a prospective material for solid-state hydrogen storage and clean energy carriers,their high operating temperature and slow kinetics are the main challenges for practical application.Here,a Mg-Ni based hydride,Mg_(2)NiH_(4) nanoparticles(~100 nm),with dual modification strategies of nanosizing and alloying is successfully prepared via a gas-solid preparation process.It is demonstrated that Mg_(2)NiH_(4) nanoparticles form a unique chain-like structure by oriented stacking and exhibit impressive hydrogen storage performance:it starts to release H2 at~170℃ and completes below 230℃ with a saturated capacity of 3.32 wt%and desorbs 3.14 wt% H_(2) within 1800 s at 200℃.The systematic characterizations of Mg_(2)NiH_(4) nanoparticles at different states reveal the dehydrogenation behavior and demonstrate the excellent structural and hydrogen storage stabilities during the de/hydrogenated process.This research is believed to provide new insights for optimizing the kinetic performance of metal hydrides and novel perspectives for designing highly active and stable hydrogen storage alloys.

Hydrogen storage performance and phase transformations in as-cast and extruded Mg-Ni-Gd-Y-Zn-Cu alloys

Thermal-mechanical processing of magnesium-based materials is an effective method to tailor the hydrogen storage performance.In this study,Mg-Ni-Gd-Y-Zn-Cu alloys were prepared by Direct Chill(DC)casting,with and without extrusion process.The influences of microstructure evolution,introduced by DC casting and thermal-mechanical processing,on the hydrogen storage performance of Mg-Ni-Gd-Y-ZnCu alloys were comprehensively explored,using analytical electron microscopy and in-situ synchrotron powder X-ray diffraction.The result shows that the extruded alloy yields higher hydrogen absorption capacity and faster hydrogen ab/desorption kinetics.As subjected to extrusion processing,theα-Mg grains in the microstructure were significantly refined and a large number of 14H type long-period stacking ordered(LPSO)phases appeared on theα-Mg matrix.After activation,there were more nanosized Gd hydride/Mg2Ni intermetallics and finer chips.These modifications synergistically enhance the hydrogen storage properties.The findings have implications for the alloy design and manufacturing of magnesiumbased hydrogen storage materials with the advantages of rapid mass production and anti-oxidation.

Electrochemical hydrogen storage performances of the nanocrystalline and amorphous(Mg_(24)Ni_(10)Cu_2)_(100–x)Nd_x(x=0–20) alloys applied to Ni-MH battery

Melt spinning technology was used to prepare the Mg2 Ni-type（Mg24 Ni10 Cu2）100–x Ndx（x=0,5,10,15,20） alloys in order to obtain a nanocrystalline and amorphous structure.The effects of Nd content and spinning rate on the structures and electrochemical hydrogen storage performances of the alloys were investigated.The structure characterizations of X-ray diffraction（XRD）,transmission electron microscopy（TEM） and scanning electron microscopy（SEM） linked with energy dispersive spectroscopy（EDS） revealed that the as-spun Nd-free alloy displayed an entire nanocrystalline structure,whereas the as-spun Nd-added alloys held a nanocrystalline and amorphous structure and the degree of amorphization visibly increased with the rising of Nd content and spinning rate,suggesting that the addition of Nd facilitated the glass forming of the Mg2 Ni-type alloy.The electrochemical measurements indicated that the addition of Nd and melt spinning improved the electrochemical hydrogen storage performances of the alloys significantly.The discharge capacities of the as-cast and spun alloys exhibited maximum values when Nd content was x=10,which were 86.4,200.5,266.3,402.5 and 452.8 mAh/g corresponding to the spinning rate of 0（As-cast was defined as the spinning rate of 0 m/s）,10,20,30 and 40 m/s,respectively.The cycle stability（S20,the capacity maintain rate at 20thcycle） of the as-cast alloy always rose with the increasing of Nd content,and those of the as-spun alloys exhibited the maximum values for Nd content x=10,which were 77.9%,83.4% 89.2% and 89.7%,corresponding to the spinning rate of 10,20,30 and 40 m/s,respectively.

Improving hydrogen storage performance of Li–Mg–N–H system by adding niobium hydride

Hydrogen storage MgH2-xNbH （x = 0 and 0.05） properties of 2LiNH2- composites and the catalysis of NbH on hydrogen sorption reaction of the Li-Mg- N-H system were investigated. Hydrogen sorption properties of 2LiNH2-MgH2 system are effectively improved by adding NbH. Temperature programmed desorption results show the addition of NbH reduces the dehydriding onset temperature of 2LiNH2-MgH2 system by 21 K. Approximate 3.62 wt% hydrogen in 2LiNH2-MgHz- 0.05NbH composite is released following a 500 min at 433 K, whereas the amount of hydrogen desorption is only -3.16 wt% for the pristine system under the same condition. The sample with NbH exhibits higher dehydriding rate compared with the pristine one. Moreover, hydrogen absorption rate increases by adding NbH into the 2LiNH2- MgH2 system. Hydrogen absorption capacity of the samples with NbH is 3.23 wt% within 400 rain, which is higher than that of pristine sample. Fine NbH particles homogeneously distribute in the 2LiNH2-MgH2-0.05NbH composite, and catalyze the hydrogen sorption reaction rather than reacts as a reactant into new compound.

Effect of lanthanum hydride on microstructures and hydrogen storage performances of 2LiNH_2-MgH_2 system

Hydrogen storage properties of 2LiNH2-MgH2 system were improved by adding lanthanum hydride （LaH3）, and the role of LaH3 in hydrogen sorption process of Li-Mg-N-H system was investigated. Temperature programmed sorption results showed that the addition of lanthanum hydride reduced the dehydriding/hydriding onset temperature of 2LiNH2-MgH2 system by at least 15 K. Moreover, A 0.053 wt.%/min average rate was determined for the hydrogen desorption of 2LiNH2-MgH2-0.05LaH3 composite, while it was only 0.035 wt.%/min for 2LiNH2-MgH2 system. Hydrogen absorption capacity increased from 1.62 wt.% to 2.12 wt.% within 200 min by adding LaH3 into 2LiNH2-MgH2 system at 383 K. In the dehydrogenation of 2LiNH2-MgH2-0.05LaH3 composite, LaH2 transferred to LaN phase, which reversed to LaH2 in the following hydrogen adsorption process. The reversible reaction of LaH2 ef- fectively promoted the hydrogen sorption of Li-Mg-N-H system. Moreover, the homogenous distribution of fine La hydride was fa- vorable to improving effect of lanthanum hydride.

Nanostructured MXene-based materials for boosting hydrogen sorption properties of Mg/MgH_(2)

Hydrogen holds the advantages of high energy density,great natural abundance and zero emission,making it suitable for large scale and long term energy storage,while its safe and efficient storage is still challenging.Among various solid state hydrogen storage materials,MgH_(2) is promising for industrial applications due to its high gravimetric and volumetric hydrogen densities and the abundance of Mg on earth.However,the practical application of MgH_(2) has been limited by its stable thermodynamics and slow hydrogen desorption kinetics.Nanocatalysis is considered as a promising approach for improving the hydrogen storage performance of MgH_(2) and bringing it closer to the requirements of commercial applications.It is worth mentioning that the recently emerging two-dimensional material,MXene,has showcased exceptional catalytic abilities in modifying the hydrogen storage properties of MgH_(2).Besides,MXene possesses a high surface area,excellent chemical/physical stability,and negatively charged terminating groups,making it an ideal support for the"nanoconfinement"of MgH_(2) or highly active catalysts.Herein,we endeavor to provide a comprehensive overview of recent investigations on MXene-based catalysts and MXene supports for improving the hydrogen sorption properties of Mg/MgH_(2).The mechanisms of hydrogen sorption involved in Mg-MXene based composites are highlighted with special emphases on thermodynamics,kinetics,and catalytic behaviors.The aim of this work is to provide a comprehensive and objective review of researches on the development of high-performance catalysts/supports to improve hydrogen storage performances of Mg/MgH_(2) and to identify the opportunities and challenges for future applications.

Recent Advances on Preparation Method of Ti-Based Hydrogen Storage Alloy

Ti-based hydrogen storage alloy is one of the most common solid-state hydrogen storage materials due to its high hydrogen absorption capacity, low dehydrogenation temperature and rich resources. This paper mainly presents the influence of several different preparation methods of Ti-based hydrogen storage alloys on the hydrogen storage performance including traditional preparation methods (smelting, rapid quenching and mechanical alloying) and novel methods by plastic deformation (cold rolling, equal channel angular pressing and high-pressure torsion). The microstructure analysis and hydrogen storage properties of Ti-based alloy are summarized thoroughly corresponding with the preparation processes mentioned above. It was found that slight introduction of lattice defects including dislocation, grain boundary, sub-grain boundary and cracks by severe plastic deformation (SPD) was beneficial to improve the hydriding/dehydriding kinetic characteristic. However, the nonuniform composition and residual stress of the alloy may be caused by SPD, which is not conducive to the improvement of hydrogen storage capacity. In the future, it would be expected that new methods and technologies combined with dopant and modification are applied to Ti-based hydrogen storage alloys to make breakthroughs in practical application.

Effect of Y,Al Co‑Doping on Hydrogen Storage Properties of La–Mg–Ni‑Based Alloys

La–Mg–Ni-based hydrogen storage alloys have excellent hydrogen storage properties.This work reports the hydrogen storage performance of a series of A_(2)B_(7)-type La_(0.96)Mg_(0.04)N_(i3.34)Al_(0.13)alloy and La_(0.96-x)Y_(x)Mg_(0.04)Ni_(3.47–0.6x)Al_(0.6x)(x=0,0.22,0.33,0.44)alloys,and explores the effect of Y and Al element combined substitution on the microstructure and hydrogen storage performance of A_(2)B_(7)-type La–Mg–Ni-based alloys.The alloys are composed of Ce_(2)Ni_(7)phase and LaNi_(5)phase.With the increase of x,the cell volume of Ce_(2)Ni_(7)phase decreases,while that of LaNi_(5)phase increases,indicating that Y atom mainly enters Ce_(2)Ni_(7)phase and Al atom mainly enters LaNi_(5)phase.An appropriate amount of co-substitution increases the hydrogen storage capacity and reduces the hydrogen absorption/desorption plateau pressure hysteresis of the alloy.When x=0.44,the hydrogen storage capacity of the alloy is 1.449 wt%,and the hysteresis coefficient is 0.302.The cell volume of Ce_(2)Ni_(7)phase and LaNi_(5)phase expands to different degrees after 20 absorption/desorption cycles.With the increase of x,the volume expansion rate decreases,and the cycle capacity retention rate also gradually decreases.This is related to the amorphization of Ce_(2)Ni_(7)phase.When x=0.22,the capacity retention rate of the alloy is 91.4%.

Synthesis of highly stable Ni nanoparticles via electrostatic self-assembly for enhanced hydrogen storage of MgH_(2)

Magnesium-based hydrides have been widely recognized as an appropriate choice for solid-state hydrogen storage.However,its undesirable thermodynamics and sluggish hydrogenation/dehydrogenation kinetics are major bottlenecks for its application.Herein,a highly stable and highly dispersed Ni-based catalyst(Ni/Al_(2)O_(3)/GN)was fabricated to promote the hydrogen storage performance of MgH_(2)via the electrostatic effect of NiAl-LDH/GN precursor with a co-calcination reduction process.MgH_(2)-5wt%Ni/Al_(2)O_(3)/GN exhibits excellent hydrogen storage performance,releasing about 5.7 wt%hydrogen in 3500 s at 250℃,and can reach a saturation hydrogen absorption of about 6.15 wt%in 3000 s at 100℃.Furthermore,it also shows low dehydrogenation apparent activation energy of 89.1 and 118.2 kJ·mol^(-1).Impressively,the catalyst ensures the stability of both the physical phase and structure during ball milling and cycling process.The role of each phase in Ni/Al_(2)O_(3)/GN on the hydrogen storage performance of MgH_(2)was also discussed through experiments and theoretical calculation,and the synergistic catalytic mechanism of Ni/Al_(2)O_(3)/GN was clearly elaborated.This work provides a unique perspective for the preparation of highly stable and highly dispersible catalysts.

Structure and electrochemical hydrogen storage characteristics of Ce-Mg-Ni-based alloys synthesized by mechanical milling

The substituting Mg with Ni and milling as-cast alloy with Ni were adopted to obtain nanocrystalline/amorphous CeMgnNi＋x wt.%Ni（x=100,200） alloys and promote the electrochemical hydrogen storage performances of CeMg_（12）-type alloys.Analyzing the structural features of the alloys provided a mechanism for ameliorating the electrochemical hydrogen storage properties.The electrochemical tests demonstrated that all the alloys just needed one cycle to be activated.Rising Ni proportion had an obvious role on charge-discharge reaction.The discharge capacities of the as-milled（60 h） alloys increased sharply from 182.0 mAh/gfor x=100 alloy to 1010.2 mAh/gfor x=200 alloy at current density of 60 mAh/g.Furthermore,milling time largely determined the performances of electrochemical reaction.The discharge capacity continued to grow along with prolonging milling time,while the cycle stability obviously decreased for x=100 alloy,and first declined and then augmented for the x=200 alloy with milling time extending.In addition,there was an optimal value with milling time varying for the high rate discharge abilities（HRD）,which was 80.3%for x=100 alloys and 86.73%for x=200,respectively.

Facile synthesis of a Ni_(3)S_(2)@C composite using cation exchange resin as an efficient catalyst to improve the kinetic properties of MgH_(2)

Carbon materials have excellent catalytic effects on the hydrogen storage performance of MgH2. Here, carbon-supported Ni3S2(denoted as Ni3S2@C) was synthesized by a facile chemical route using ion exchange resin and nickel acetate tetrahydrate as raw materials and then introduced to improve the hydrogen storage properties of MgH2. The results indicated the addition of 10 wt.% Ni3S2@C prepared by macroporous ion exchange resin can effectively improve the hydrogenation/dehydrogenation kinetic properties of MgH2. At 100 ℃,the dehydrogenated MgH2-Ni3S2@C-4 composite could absorb 5.68 wt.% H2. Additionally, the rehydrogenated MgH2-Ni3S2@C-4 sample could release 6.35 wt.% H2at 275 ℃. The dehydrogenation/hydrogenation enthalpy changes of MgH2-Ni3S2@C-4 were calculated to be 78.5 k J mol-1/-74.7 k J mol-1, i.e., 11.0 k J mol-1/7.3 k J mol-1lower than those of MgH2. The improvement in the kinetic properties of MgH2was ascribed to the multi-phase catalytic action of C, Mg2Ni, and Mg S, which were formed by the reaction between Ni3S2contained in the Ni3S2@C catalyst and Mg during the first hydrogen absorption–desorption process.

Structure and electrochemical properties of LaMgNi4-xCox(x=0-0.8)hydrogen storage electrode alloys

LaMgNi（4-x）Cox（x = 0-0.8） electrode alloys used for MH/Ni batteries were prepared by induction melting. The structures and electrochemical hydrogen storage properties of the alloys were investigated in detail.X-ray diffraction（XRD） and scanning electron microscopy（SEM） analysis show that LaMgNi4 phase and LaNi5 phase are obtained. The lattice parameters of the two phases increase first and then decrease with Co content increasing.The electrochemical properties of the alloy electrodes were measured by means of simulated battery tests. Results show that the addition of Co does not change the discharge voltage plateau of the alloy electrodes. However, the maximum discharge capacity increases from 319.9 mAh·g^-1（x = 0）to 347.5 mAh·g^-1（x = 0.4） and then decreases to331.7 mAh·g^-1（x = 0.8）. The effects of Co content on electrochemical kinetics of the alloy electrodes were also performed. The high rate dischargeability（HRD） first increases and then decreases with Co content increasing and reaches the maximum value（95.0 %） when x = 0.4. Test results of the electrochemical impedance spectra（EIS）,potentiodynamic polarization curves and constant potential step measurements of the alloy electrodes all demonstrate that when Co content is 0.4 at%, the alloy exhibits the best comprehensive electrochemical properties.

Effect of annealing treatment on hydrogen storage properties of La-Ti-Mg-Ni-based alloy

The present study dealt with investigations on the effects of annealing on the hydrogen storage properties of La 1.6 Ti 0.4 MgNi 9 alloys.The experimental alloys were prepared by magnetic levitation melting followed by annealing treatment.For La 1.6 Ti 0.4 MgNi 9 alloys,LaNi 5,LaNi 3 and LaMg 2 Ni 9 were the main phases,Ti 2 Ni phase appeared at 900℃.Annealing not only enhanced the maximum and effective hydrogen storage capacity,improved the hydrogen absorption/desorption kinetics,but also increased the discharge capacity.The cyclic stability had been improved markedly by annealing,e.g.,when the discharge capacity reduced to 60% of maximum discharge capacity,the charge/discharge cycles increased from 66（as-cast） to 89（annealed at 800℃） and 127 times（annealed at 900℃）.La 1.6 Ti 0.4 MgNi 9 alloy annealed at 900℃ exhibited better electrochemical properties compared to the other two alloy electrodes.

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.