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).

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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）.

Effect of LaFeO_3 on hydrogenation/dehydrogenation properties of MgH_2

LaFeO3 was used to improve the hydrogen storage properties of Mg H2. The Mg H2＋20 wt.%La Fe O3 composite was prepared by ball milling method. The composite could absorb 3.417 wt.% of hydrogen within 21 min at 423 K while Mg H2 only uptaked 0.977 wt.% hydrogen under the same conditions. The composite also released 3.894 wt.% of hydrogen at 623 K, which was almost twice more than Mg H2. The TPD measurement showed that the onset dissociation temperature of the composite was 570 K, 80 K lower than the Mg H2. Based on the Kissinger plot analysis of the composite, the activation energy E des was estimated to be 86.69 k J/mol, which was 36 k J/mol lower than Mg H2. The XRD and SEM results demonstrated that highly dispersed La Fe O3 could be presented in Mg H2, benefiting the reduction of particle size and also acting as an inhibitor to keep the particles from clustering during the ball-milled process.

Influence of magnesium on electrochemical properties of RE_(3-x)Mg_x(Ni_(0.7)Co_(0.2)Mn_(0.1))_9(x=0.5-1.25) alloy electrodes

RE3-xMgx（Ni0.7Co0.2Mn0.1）9 （x=0.5-1.25） alloys were prepared by induction melting and the influence of the partial substitution of RE （where RE stands for La-rich mischmetal） by Mg on the hydrogen storage and electrochemical properties of the alloys were investigated systematically. These alloys mainly consisted of three phases, La（Ni,Mn,Co）5 phase, La2Ni7 phase and Mg2Ni phase. The P-C-T isotherms showed that with Mg content increasing in the aUoys, the hydrogen storage capacity first increased and reached the maximum capacity of 1.36 wt.% when x=1.0, and then decreased with x increasing fiarther. Electrochemical studies revealed that the discharge capacity reached the maximum value of 380 mAh/g and the alloy electrode presented better cyclic stability when RE/Mg=2. The high rate discharge ability of the alloy electrodes was also improved by the substitution of Mg for RE. The RE2Mg（Ni0.7CO0.2Mno.09 alloy exhibited better hydrogen absorption kinetics （x= 1.0）.

Study on electrochemical property of La_(0.75)Mg_(0.25)Ni_(2.85)Co_(0.45–x)(AlSn)_x (x=0.0,0.1,0.2,0.3) alloys

La_（0.75）Mg_（0.25）Ni_（2.85）Co_（0.45–x）（AlSn）_x（AlSn）_x（x=0.0,0.1,0.2,0.3） alloys were prepared by magnetic induction melting method, and the phase composition and electrochemical properties were investigated systematically. The alloys were mainly composed of LaNi5, La2Ni7 and LaNi3 phase, and the cell volume of LaNi5 increased with the Al and Sn contents. For the alloy corresponding to x=0.0, the Cmax and C150 were 348.9 and 185 mA h/g, respectively, then for the alloy electrode with x=0.2, even though the Cmax was only 309.0 mA h/g less than 348.9 mA h/g, the C150 of 231 mA h/g was much higher than 185 mA h/g. And the values of the limit current density, anodic peak current density and hydrogen diffusion coefficient of the La0.75Mg0.25Ni2.85Co0.35（AlS n）0.1（x=0.1） alloy were 1079.5, 1023.8 mA /g and 5.71×10–10 cm2/s, respectively. Which were the highest than that of any other electrodes. These results suggested that the kinetic property of the La_（0.75）Mg_（0.25）Ni_（2.85）Co_（0.45–x）（AlSn）_x（AlSn）_x（x=0.0, 0.1, 0.2, 0.3） electrodes could be improved effectively by adding moderate contents of Al and Sn.