Graphene-loaded nickel−vanadium bimetal oxides as hydrogen pumps to boost solid-state hydrogen storage kinetic performance of magnesium hydride

To modify the thermodynamics and kinetic performance of magnesium hydride(MgH_(2))for solid-state hydrogen storage,Ni_(3)V_(2)O_(8)-rGO(rGO represents reduced graphene oxide)and Ni_(3)V_(2)O_(8)nanocomposites were prepared by hydrothermal and subsequent heat treatment.The beginning hydrogen desorption temperature of 7 wt.%Ni_(3)V_(2)O_(8)-rGO modified MgH_(2)was reduced to 208℃,while the additive-free MgH_(2)and 7 wt.%Ni_(3)V_(2)O_(8)doped MgH_(2)appeared to discharge hydrogen at 340 and 226℃,respectively.A charging capacity of about 4.7 wt.%H_(2)for MgH_(2)+7 wt.%Ni_(3)V_(2)O_(8)-rGO was achieved at 125℃ in 10 min,while the dehydrogenated MgH_(2)took 60 min to absorb only 4.6 wt.%H_(2)at 215℃.The microstructure analysis confirmed that the in-situ generated Mg_(2)Ni/Mg_(2)N_(i)H_(4) and metallic V contributed significantly to the enhanced performance of MgH_(2).In addition,the presence of rGO in the MgH_(2)+7 wt.%Ni_(3)V_(2)O_(8)-rGO composite reduced particle aggregation tendency of Mg/MgH_(2),leading to improving the cyclic stability of MgH_(2)during 20 cycles.

Preparation of ZrMn_2 hydrogen storage alloy by electro-deoxidation in molten calcium chloride

ZrMn2 alloy was electro-synthesized directly from cathode pellets compacted with powdered mixture of MnO2 and ZrO2 in molten calcium chloride. Sintering temperature, cell voltage and electrolysis time were the dominant factors that affected the characteristics of the final product. The results confirmed the formation of pure ZrMn2 alloy through the electro-deoxidation of the mixed oxide pellets at 3.1 V for 12 h in 900 °C CaCl2 melt. The X-ray diffraction（XRD） and cyclic voltammetry analysis suggested that the electro-deoxidation proceeded from the reduction of manganese oxides to Mn, followed by ZrO2 or CaZrO3 reduction on the pre-formed Mn to ZrMn2 alloy. The cyclic voltammetry measurements using powder microelectrode showed that the prepared ZrMn2 alloy has a good electrochemical hydrogen storage property.

Effect of Ni,Fe and Fe-Ni alloy catalysts on the synthesis of metal contained carbon nano-onions and studies of their electrochemical hydrogen storage properties

Three types of carbon nano-onions（CNOs） including Ni@CNOs.Fe3C@CNOs and Fe0.64Ni0.36@CNOs nanoparticles have been synthesized by catalytic decomposition of methane at 850 ℃ using nickel,iron and iron-nickel alloy catalysts.Comparative and systematic studies have been carried out on the morphology,structural characteristics and graphitic crystallinity of these CNOs products.Furthermore,the electrochemical hydrogen storage properties of three types of CNOs have been investigated.Measurements show that the Ni@CNOs have the highest discharge capacity of 387.2 mAh/g,coiTesponding to a hydrogen storage of 1.42%.This comparison study shows the advantages of each catalyst in the growth of CNOs.enabling the controllable synthesis and tuning the properties of CNOs by mediating different metals and their alloy for using in the fuel cell system.

Hydrogen Storage Properties of Ti_(1.2)Fe+xCa Hydrogen Storage Alloys

The hydrogen storage properties of Ti1.2Fe+xCa (x=1%, 3% and 5% in mass fraction) alloys was investigated. Results stow that the modified alloys can be activated without any thermal treatment at room temperature due to the addition of Ca and excess Ti in (lie alloys. Hydrogen storage properties of these modified alloys vary with Ca amount and reaction temperature. In addition, the influence mechanism of the addition of Ca and excessive Ti on the activation behavior and hydrogen storage capacity of the alloys was discussed.

Characteristics of Hydrogen Storage Alloy Mg_2Ni Produced by Hydriding Combustion Synthesis

A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigated by means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showed that the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis without any activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp (0.1 MPa)=-3026/T+5.814 (523 K≤T≤623 K) for hydriding and Igp (0.1 MPa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1-a)]3/2 = kt and the apparent activation energy for the nucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31kJ/(mol.H2) and 59.9±2.99kJ/(mol.H2)respectively.

HYDROGEN STORAGE PROPERTIES OF Mg MODIFIED WITH TETRAHYDROFURAN

The hydriding and dehydriding behaviors of tetrahydrofuran modified Mg,its electronic struc- ture,crystal structure,micro-morphology as well as its stability have been investigated.The modifield Mg absorbs 3.5 wt-％ hydrogen at 643 K in 3.5 MPa H_2,its hydride gives off 3.2 wt-％ hydrogen at 643 K in a vaccum of 1.3 Pa after 20 cycles of hydriding and dehydriding. Tetrahydrofuran alters the electronic structure of Mg but keeps its crystal strueture unchanged.In hydriding products,a new hydride phase is found in addition to the known MgH_2 phase.The hydride formed from Mg is polv-erystalline.The wide-spreading slip bands and twins within crystals indicate that the transformation during absorption of hydrogen causes serious lattice distortions.

Effect of Ti substitution on hydrogen storage properties of Zr_(1-x)Ti_xCo (x = 0, 0.1, 0.2, 0.3) alloys

Zr1-xTixCo(x = 0, 0.1, 0.2, 0.3) alloys were prepared by arc-melting method and the effect of Ti substitution on hydrogen storage properties was studied systematically. Hydrogen desorption pressure-composition-temperature(PCT) measurements were carried out using Sievert’s type volumetric apparatus for ZrCo(at 473 K, 573 K and 673 K) and Zr1-xTixCo alloys(at 673 K), respectively. Products after dehydrogenation were characterized by X-ray diffraction(XRD). In addition, the kinetics of Zr1-xTixCo hydride was investigated at 473 K and 673 K,respectively, under hydrogen pressure of 5 MPa. Results showed that Ti substitution for Zr did not change the crystal structure of ZrCo phase.With the increase of temperature from 473 K to 673 K, the extent of disproportionation for ZrCo alloy increased. With Ti content increasing at 673 K, the desorption equilibrium pressure of Zr1-xTixCo-H2 systems elevated and the disproportionation reaction of Zr1-xTixCo alloys was inhibited effectively. Ti substitution decreased the kinetics rate and the effective hydrogen storage capacity of Zr1-xTixCo alloys slightly.Generally speaking, it was found that Zr0.8Ti0.2Co alloy had better anti-disproportionation property with less decrease of effective hydrogen storage capacity which was beneficial to tritium application in the International Thermonuclear Experimental Reactor(ITER).

Hydrogen storage properties of magnesium hydride catalyzed by Ni-based solid solutions

The Ni−25%X(X=Fe,Co,Cu,molar fraction)solid solutions were prepared and then doped into MgH_(2) through high-energy ball milling.The initial dehydrogenation temperatures of MgH_(2)/Ni−25%X composites are all decreased by about 90℃relative to the as-milled pristine MgH_(2).The Ni−25%Co solid solution exhibits the most excellent catalytic effect,and the milled MgH_(2)/Ni−25%Co composite can release 5.19 wt.%hydrogen within 10 min at 300℃,while the as-milled pristine MgH_(2) can only release 1.78 wt.%hydrogen.More importantly,the dehydrogenated MgH_(2)/Ni−25%Co composite can absorb 5.39 wt.%hydrogen at 275℃within 3 min.The superior hydrogen sorption kinetics of MgH_(2)/Ni−25%Co can be ascribed to the actual catalytic effect of in-situ formed Mg_(2)Ni(Co)compounds.First-principles calculations show that the hydrogen absorption/desorption energy barriers of Mg/MgH_(2) systems decrease significantly after doping with transition metal atoms,which interprets well the improved hydrogen sorption properties of MgH_(2) catalyzed by Ni-based solid solutions.

Phase structure and hydrogen storage properties of LaMg_(3.70)Ni_(1.18) alloy

The phase structure and hydrogen storage properties of LaMg 3.70 Ni 1.18 alloy were investigated. The LaMg 3.70 Ni 1.18 alloy consists of main LaMg 2 Ni phase, minor La 2 Mg 17 and LaMg 3 phases. The alloy can be activated in the first hydriding/dehydriding process, and initial LaMg 2 Ni, La 2 Mg 17 , and LaMg 3 phases transfer to LaH 2.34 , Mg, and Mg 2 Ni phases after activation. The reversible hydrogen storage capacity of the LaMg 3.70 Ni 1.18 alloy is 2.47 wt.% at 558 K, which is higher than that of the LaMg 2 Ni alloy. The pressure-composition-temperature （PCT） curves display two hydriding plateaus, corresponding to the formation of MgH 2 and Mg 2 NiH 4 . However, only one dehydriding plateau is observed, owing to the synergetic effect of hydrogen desorption between MgH 2 and Mg 2 NiH 4 . The uptake time for hydrogen content to reach 99% of saturated state is less than 250 s, and 90% hydrogen can be released in 1200 s in the experimental conditions, showing fast kinetics in hydriding and dehydriding. The activation energies of the LaMg 3.70 Ni 1.18 alloy are –51.5 ± 1.1 kJ/mol and –57.0 ± 0.6 kJ/mol for hydriding and dehydriding, respectively. The hydriding/dehydriding kinetics of the LaMg 3.70 Ni 1.18 alloy is better than that of the Mg 2 Ni alloy, owing to the lower activation energy values.

Hydrogen storage properties of Mg(Al)solid solution alloy doped with LaF_(3) by ball milling

LaF_(3) was doped to the Mg(Al)solid solution alloy for enhancing the hydrogen absorption and desorption by ball milling.XRD was used to analyze the phases of the samples and the phase transition induced by hydrogenation and dehydrogenation.The microstructure and phase distribution were investigated by SEM and STEM.The hydrogen storage properties were measured by Sieverts method.For Mg_(0.93)Al_(0.07)−5wt.%LaF_(3) nanocomposite,the hydrogen storage kinetic properties were significantly improved by reducing the hydriding and dehydriding activation energies to 65 and 78 kJ/mol,respectively,and the dehydriding enthalpy was calculated to be 69.7 kJ/mol.The improved hydrogen storage properties were mainly attributed to the catalytic effects of the in situ formed nanostructure Al_(11)La_(3) and MgF_(2) together with the dissolving of Al in Mg lattice.

Hydrogen storage behaviors and microstructure of MF_3(M=Ti,Fe)-doped magnesium hydride

MgH2+10%MF3(M=Ti,Fe)(mass fraction) composites were prepared by ball-milling in hydrogen atmosphere,and their hydrogen storage behaviors and microstructure were investigated systematically.The results show that the hydriding and dehydriding kinetics of MgH2 are markedly improved by doping TiF3 and FeF3 fluorides.At 573 K,the two composites can absorb 5.67%-6.07%(mass fraction) hydrogen within 5 min under an initial hydrogen pressure of 3.5 MPa,and desorb 5.34%-6.02% hydrogen within 6 min.Furthermore,the composites can absorb hydrogen rapidly in moderate temperature range of 313-473 K.In comparison,TiF3-doped sample has a better hydriding-dehydriding kinetics than FeF3-doped sample.The microstructure analysis shows that some active particles including MgF2,TiH2 and Fe could be formed in the hydriding-dehydriding processes of the MF3-doped composites.From the Kissinger's plot,the apparent activation energies for the hydrogen desorption of the composites are estimated to be 74.1 kJ/mol for TiF3-doped composite and 77.6 kJ/mol for FeF3-doped composite,indicating MgH2 is significantly activated due to the catalytic effect of the doping of MF3.

Enhanced dehydrogenation kinetic properties and hydrogen storage reversibility of LiBH_4 confined in activated charcoal

LiBH4 was confined into activated charcoal（AC） by melt infiltration method（MI）, and its effects on the hydrogen sorption properties were investigated. The N2 adsorption results reveal that melt infiltration method can effectively incorporated LiBH4 into AC. It can maintain the structural integrity of the scaffold and ensure the confinement effect. The nano-confined LiBH4/AC starts to release hydrogen at around 190 °C, which is 160 °C lower than that of pure LiBH4, and reaches a hydrogen desorption capacity of 13.6% at 400 °C. When rehydrogenated under the condition of 6 MPa H2 and 350 °C, it has a reversible hydrogen storage capacity of 6%, while pure LiBH4 shows almost no reversible hydrogen storage capacity under the same condition. Mass spectrometry analysis（MS） results suggest that no diborane or other impurity gases are released in the decomposition process. The apparent activation energy of dehydrogenation of LiBH4 after confinement into AC decreases from 156.0 to 121.1 k J/mol, which leads to the eminent enhancement of dehydrogenation kinetics of LiBH4.

A_(2)B_(7)-type La-Mg-Ni alloys prepared by Mg thermal diffusion for improved hydrogen storage performance

A novel approach based on thermal diffusion was used to achieve controllable Mg content in A_(2)B_(7)-type La-Mg-Ni-based alloys.The formation mechanism of the A_(2)B_(7)-type phase as a result of the thermal diffusion process and the effect of Mg content on hydrogen storage performance were investigated.X-ray diffraction(XRD)patterns and Rietveld refinement results showed that increased Mg transformed the LaNi_(5)phase in the La_(0.74)Sm_(0.03)Y_(0.23)Ni_(4.32)Al_(0.04)precursor alloy into a superlattice structure.Scanning electron microscopy(SEM)images showed that Mg was evenly distributed in the alloy bulk.Mg in the superlattice significantly inhibited the phase decomposition of the superlattice structure during the hydrogen absorption/desorption cycles.An A_(2)B_(7)-type La_(0.57)Sm_(0.02)Y_(0.18)Mg_(0.23)Ni_(3.38)Al_(0.03)alloy composed of Gd_(2)Co_(7)and Ce_(2)Ni_(7)phases was successfully synthesized.The pressure-composition isotherm profiles showed that the alloy had a hydrogen storage capacity as high as 1.73 wt%,with good cycling stability.After 50 cycles of hydrogen absorption/desorption,the alloy retained a hydrogen storage capacity of 1.45 wt%,with a capacity retention rate of up to 84.28%.The Mg thermal diffusion process thus provides a new approach for the controlled preparation of La-Mg-Ni-based alloys.

Phase component and microstructure of laser-sintered Mg-Ni alloys

The Mg-Ni hydrogen storage alloys were prepared using the laser sintering technology. The effects of laser sintering power on the phase component and the weight loss of Mg element for the Mg-Ni alloys were investigated. The samples P1, P2 and P3 consisted of five phases： Mg2Ni, MgNi2, Mg, Ni and MgO. The weight loss of Mg element remarkably increased at 1200 W. The addition of extra Mg significantly promoted the reaction between Mg and Ni. Mg2Ni, MgNi2, and a small amount of Ni and MgO phases were present in the samples PM （pestie milling） and BM （ball milling）. The sample PM has a homogeneous microstructure, and the contents of Mg2Ni and MgNi2 were approximately consistent with those of the Mg-Ni alloy under the equilibrium conditions. The maximum hydrogen storage capacity of the sample BM was 1.72 wt.% and the sample can be activated easily at 573 K （only 3 activation cycles）.

A study on hydrogen storage and electrochemical properties of La_(0.55)Pr_(0.05)Nd_(0.15)Mg_(0.25)Ni_(3.5) (Co_(0.5)Al_(0.5))_x (x=0.0, 0.1, 0.3, 0.5) alloys

The La0.55Pr0.05Nd0.15Mg0.25Ni3.5（Co0.5Al0.5）x（x=0.0, 0.1, 0.3, 0.5） alloys were prepared by magnetic levitation melting under an Ar atmosphere, and the effects of Co and Al on the hydrogen storage and electrochemical properties were systematically investigated by pressure composition isotherms, cyclic voltammetry, Tafel polarization and electrochemical impedance spectroscopy testing. The results showed that the alloy phases were mainly consisted of （La,Pr）（Ni,Co）5, LaMg2Ni9, （La,Nd）2Ni7 and LaNi3 phases, and the cell volumes of （La,Pr）（Ni,Co）5, LaMg2Ni9, （La,Nd）2Ni7 and LaNi3 phases expanded with Co and Al element added. The hydrogen storage capacity initially increased from 1.36 （x=0） to 1.47 wt.% （x=0.3） and then decreased to 1.22 wt.% （x=0.5）. The discharge capacity retention and cycle stability of the alloy electrodes were improved with the increase of Co and Al contents. The La0.55Pr0.05Nd0.15Mg0.25Ni3.5（Co0.5Al0.5）0.3 alloy electrode possessed better electrochemical kinetic characteristic.

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.

Synthesis of Mg-based composite material with in-situ formed LaH_3 and its hydrogen storage characteristics

In this work,a Mg-based composite material with in-situ formed LaH3, Mg2 NiH4-LiBH4 ＋ 20 wt% LaH3,was prepared by ball milling LiBH4 and hydrogenated LaMg2 Ni and Mg2 Ni powder mixture, followed by heat treatment at 573 K. The onset dehydrogenation temperature of the composite is reduced by 50 K compared with that of Mg2 NiH4-LiBH4. The LaH3-doped composite shows faster kinetics,absorbing1.43 wt% hydrogen within 100 s at 423 K,which is 6.5 times faster than Mg2 NiH4-LiBH4. Moreover,the composite releases 1.24 wt% hydrogen within 500 s at 573 K,0.69 wt% higher than Mg2 NiH4-LiBH4. The activation energy of the composite is reduced by 8.2 and 80 kJ/mol compared with that of Mg2 NiH4-LiBH4 and commercial MgH2, respectively. The improvement in hydrogen storage properties is attributed to the fact that LaH3 promotes the generation of nano-sized spongy Mg structure, which has good catalytic activity during the subsequent hydrogenation/dehydrogenation process.

Hydrogen storage properties of Nb-compounds-catalyzed LiBH4-MgH2

In order to improve the hydrogen storage properties of LiBH4-MgH2 composite, two different kinds of Nb-based catalysts, NbC and NbF5, were added to LiBH4-MgH2 composite by ball milling, and the effect of catalysts on hydrogen storage properties of the modified LiBH4-MgH2 system was investigated. The experimental results show that LiBH4-MgH2 composite is a two-step dehydrogenation process, and Nb-based compounds can remarkably enhance its dehydrogenation kinetics. For the composite without addition of catalysts, the starting decomposition temperature for the first dehydrogenation step is around 320℃, and there is a long period of incubation time（around 220 min） for the occurrence of the second decomposition step even at high temperature of 450℃. It needs more than 10 h to complete the decomposition process and release around 9 wt% H2. After addition of 5 mol% NbF5, the starting decomposition temperature for the first dehydrogenation step is around 150℃, there is no incubation time for the second decomposition step, and it takes around 40 min to complete the second step and reaches a total dehydrogenation capacity of 9.5 wt%. NbF5 has better catalytic effect than NbC. Based on the hydrogenation/dehydrogenation behaviors and structural variation, the mechanism of catalytic effect was discussed.

Influence of lanthanon hydride catalysts on hydrogen storage properties of sodium alanates

NaAlH4 complex hydrides doped with lanthanon hydrides were prepared by hydrogenation of the ball-milled NaH/Al＋ xrnol.% RE-H composites （RE=La, Ce; x=2, 4, 6） using Nail and A1 powder as raw materials. The influence of lanthanon hydride catalysts on the hydriding and dehydriding behaviors of the as-synthesized composites were investigated. It was found that the com- posite doped with 2 mol.% LaH3.01 displayed the highest hydrogen absorption capacity of 4.78 wt.% mad desorption capacity of 4.66 wt.%, respectively. Moreover, the composite doped with 6 mol% CEH2.51 showed the best hydriding/dehydriding reaction kinetics. The proposed catalytic mechanism for reversible hydrogen storage properties of the composite was attributed to the presence of active LaH3.01 and CeH2.51 particles, which were scattering on the surface of Nail and A1 particles, acting as the catalytic active sites for hydrogen diffusion and playing an important catalytic role in the improved hydriding/dehydriding reaction.

Mechanochemistry and hydrogen storage properties of 2Li_(3)N+Mg mixture

The Li-Mg-N-H hydrogen storage system is a promising hydrogen storage material due to its moderate operation temperature,good reversibility,and relatively high capacity.In this work,the Li-Mg-N-H composite was directly synthesized by reactive ball milling(RBM) of Li3N and Mg powder mixture with a molar ratio of 2:1 under hydrogen pressure of 9 MPa.More than 8.8 wt%hydrogen was absorbed during the RBM process.The phases and structural evolution during the in situ hydrogenation process were analyzed by means of in situ solidgas absorption and ex situ X-ray diffraction(XRD) measurements.It is determined that the hydrogenation can be divided into two steps,leading to mainly the formation of a lithium magnesium imide phase and a poorly crystallized amide phase,respectively.The H-cycling properties of the as-milled composite were determined by temperature-programmed dehydrogenation(TPD) method in a closed system.The onset dehydrogenation temperature was detected at 125℃,and it can reversibly desorb 3.1 wt% hydrogen under a hydrogen back pressure of 0.2 MPa.The structural evolution during dehydrogenation was further investigated by in situ XRD measurement.It is found that Mg(NH_(2))_(2)phase disappears at about 200 ℃,and Li_(2)Mg_(2)N_(3)H_(3),LiNH_(2),and Li_(2)MgN_(2)H_(2)phases coexist at even 300 ℃,revealing that the dehydrogenation process is step-wised and only partial hydrogen can be desorbed.