Properties of Ti-Based Hydrogen Storage Alloy

An efficient and safe hydrogen storage method is one of the important links for the large-scale development of hydrogen in the future. Because of its low price and simple design, Ti-based hydrogen storage alloys are considered to be suitable for practical applications. In this paper, we review the latest research on Ti-based hydrogen storage alloys. Firstly, the machine learning and density functional theory are introduced to provide theoretical guidance for the optimization of Ti-based hydrogen storage alloys. Then, in order to improve the hydrogen storage performance, we briefly introduce the research of AB type and AB2 type Ti-based alloys, focusing on doping elements and adaptive after treatment. Finally, suggestions for the future research and development of Ti-based hydrogen storage alloys are proposed. .

Effects of La substitution on microstructure and hydrogen storage properties of Ti−Fe−Mn-based alloy prepared through melt spinning

The as-spun Ti_(1−x)La_(x)Fe_(0.8)Mn_(0.2)(x=0,0.01,0.03,0.06,0.09,molar fraction)alloys were prepared by melt spinning.The effects of La substitution for Ti on the microstructure,hydrogen storage kinetics and thermodynamics of TiFe-type Ti−Fe−Mn-based alloy were investigated.The as-spun alloys hold the TiFe single phase,which transforms to TiFeH_(0.06),TiFeH,and TiFeH_(2) hydrides after hydrogenation.La substitution promotes the formation of micro-defects(such as dislocations and grain boundaries)in the alloys,thus facilitating hydrogen diffusion.In addition,the hydrogen storage kinetics properties are improved after introducing La element.With the rise of La content,the hydrogen storage capacity decreases firstly and then increases,but the absolute value of hydriding enthalpy change(|ΔH|)increases firstly and then reduces.When x=0.01,the maximum value of|ΔH|is obtained to be(25.23±0.50)kJ/mol for hydriding,and the alloy has the maximum hydrogen absorption capacity of(1.80±0.04)wt.%under the conditions of 323 K and 3 MPa.

Effect of VFe addition on hydrogen storage behavior of TiMn_(1.5)-based alloys

The hydrogen absorption and desorption behavior of TiMn_(1.25)Cr_(0.25)alloys with VFe substitution for partial Mn was investigated at 273, 293 and 313 K. It is found thatVFe substitution increases their hydrogen storage capacity, decreases the plateau pressure and thehysteresis factor of their pressure-composition-temperature (PCT) curves. After annealing treatmentat 1223 K for 6 h, TiMn_(0.95)Cr_(0.25)(VFe)_(0.3) alloy exhibits a lower hydrogen desorptionplateau pressure (0.27 MPa at 313 K) and a smaller hysteresis factor (0.13 at 313 K); the maximumand effective hydrogen storage capacities (mass fraction) are 2.03% and 1.12% respectively, whichcan satisfy the demand of hydrogen storage tanks for proton exchange membrane fuel cells (PEMFC).

Study on Particle Size and Electrochemical Properties of Rare Earth Based Hydrogen Storage Alloys

The rare earth based hydrogen storage alloys Ml_ 0.7Mm_ 0.3(Ni_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3) were chosen as objects of investigation in this paper. The effects of particle size on electrochemical properties of the alloy were investigated. The results indicate that the alloy with particle size of 100 and 150 mesh shows good activation behavior and high discharge capacity (the first discharge capacity and the maximum discharge capacity), but poor cycling stability, low capacity retention and high discharge capacity rate. The Ml_ 0.7Mm_ 0.3(Ni_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3) alloy with particle size of 150 mesh shows excellent electrochemical properties.

Phase Structure and Electrochemical Properties of Rare Earth Based Hydrogen Storage Alloys

The rare earth based hydrogen storage alloys MmxM1 1 - x ( Ni3.55 Co0.75 Mn0.4 A10.3 ) ( x = 0 ～ 0.5 ) were investigated in this work.Adjusted Ml: Mm ratio to change the content of La,Ce,Pr and Nd in the alloys and then to change the phase structure, the influences of phase structure on the electrochemical properties were analyzed.The results indicate that the main phase of all alloys is LaNi5 with CaCu5 type structure and the crystal lattices constants of LaNi5 are changed with increasing x value, i.e, decreased a-axis, increased c-axis and axis ratio and nonlinear decreased crystal volume.The crystal volume of the alloy with x = 0.3 is larger than others.There is second phase A1LaNi4 in alloys when x≥0.3, which decrease the discharge capacity, but increase the cycling stability and high rate discharge ability.Compared comprehensively, the alloy with x = 0.3 shows the higher discharge capacity and the better cycling stability.

Effect of Heat-Treatment Process on Properties of Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed . The electrochemical properties such as cycling stability, activation property, and the plateau voltage of the alloy which was heat-treated in various temperatures and times had different changes during the cycle process, the optimum heat-treatment conditions of this alloy were determined by this work.

Electrochemical properties of TiV-based hydrogen storage alloys

The electrochemical properties of the super-stoichiometric TiV-based hydrogen storage electrode alloys(Ti 0.8Zr 0.2)(V 0.533Mn 0.107Cr 0.16Ni 0.2) x(x=2, 3, 4, 5, 6) were studied. It is found by XRD analysis that all the alloys mainly consist of a C14 Laves phase with hexagonal structure and a V-based solid solution phase with BCC structure. The lattice parameters and the unit cell volumes of the two phases decrease with increasing x. The cycle life, the linear polarization, the anode polarization and the electrochemical impedance spectra of the alloy electrodes were investigated systematically. The overall electrochemical properties of the alloy electrode are found improved greatly as the result of super-stoichiometry and get to the best when x=5.

Study on Phase Structure and PCT Characteristics of Rare Earth Based Hydrogen Storage Alloys

The rare earth based hydrogen storage alloys Mm_xMl_ 1-xNi_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3(x=0～0.50) were investigated in this work. The influences of phase structure on the PCT characteristics were analyzed by means of electrochemical measurements. The results indicate that there is a strict relationship between crystal volume and PCT characteristics.

Electrochemical hydrogen storage characteristics of nanocrystalline and amorphous Mg_2Ni-type alloys prepared by melt-spinning

The nanocrystalline and amorphous Mg2Ni-type alloys with nominal compositions of Mg2Ni1-xMnx （x=0, 0.1, 0.2, 0.3, 0.4） were synthesized by melt-spinning technique. The spun alloy ribbons with a continuous length, a thickness of about 30 μm and a width of about 25 mm are obtained. The structures of the as-spun alloy ribbons were characterized by XRD and HRTEM. The electrochemical hydrogen storage characteristics of the as-spun alloy ribbons were measured by an automatic galvanostatic system. The electrochemical impedance spectrums （EIS） were plotted by an electrochemical workstation. The hydrogen diffusion coefficients （D） in the alloys were calculated by virtue of potential-step measurement. The results show that all the as-spun （x=0） alloys hold a typical nanocrystalline structure, whereas the as-spun （x=0.4） alloy displays a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni facilitates the glass formation in the Mg2Ni-type alloy. The substitution of Mn for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, involving the discharge capacity and the electrochemical cycle stability. With an increase in the amount of Mn substitution from 0 to 0.4, the discharge capacity of the as-spun （20 m/s） alloy increases from 96.5 to 265.3 mA·h/g, and its capacity retaining rate （S20） at the 20th cycle increases from 31.3% to 70.2%. Furthermore, the high rate dischargeability （HRD）, electrochemical impedance spectrum and potential-step measurements all indicate that the electrochemical kinetics of the alloy electrodes first increases then decreases with raising the amount of Mn substitution.

Cluster-based composition rule for Laves phase-related BCC solid solution hydrogen storage alloys

A new cluster line approach for the composition rule of Laves phase-related BCC solid solution hydrogen-storage alloys was presented. The cluster line in a ternary phase diagram refers to a straight composition line linking a specific binary cluster to the third element. In the Laves phase-related BCC solid solution alloy system such as Ti-Cr-V, Ti-Cr tends to form binary Cr2Ti Laves phase while Ti-V and Cr-V to form solid solutions. This Laves phase is characterized by a close-packing icosahedral cluster Cr7Ti6. A cluster line Cr7Ti6-V is then constructed in this system. Alloy rods with a diameter of 3 mm of compositions along this line were prepared by copper-mould suction method. The alloy structure is found to vary with the V contents. Furthermore, the P-C-T measurements indicate that the cluster-line (Cr7Ti6)1-xVx alloys have large hydrogen storage capacities.

Effects of Mn content on microstructure and electrochemical properties of LaNi_(4.2-x)Co_(0.6)Mn_xAl_(0.2)(x=0-0.2) hydrogen storage alloys

The effects of Mn content on microstructure and electrochemical properties of LaNi4.2-xCo0.6MnxAl0.2 alloys were investigated systematically. The results of XRD analyses indicate that the substitution of Mn does not change the crystal structure,but along with the increase of Mn substitution quantity,the volume of the crystal increases and the ratio of axial to radial lattice parameters(a/c) first increases,then decreases. With the increase of Mn substitution quantity in LaNi4.2-xCo0.6Mnx Al0.2,the discharge capacity,charge efficiency,the self-discharge and high rate discharge capacity increase first and then decrease. The discharge capacity reaches the highest value of 367 mA·h/g(x=0.1) at 0.2C.

Hydrogen storage properties of V+ TiFe_(0.85) Mn_(0.15) multi-phase alloys made by mechanical alloying

The mechanical alloying technique was used to make multi phase alloys V+ TiFe 0.85 Mn 0.15 . Their hydrogen storage properties were characterized and compared with that of the polycrystalline alloys made by casting. It was found that the ball milled alloys can absorb hydrogen at room temperature in the first cycle without prior activation. The 40%V + 60% TiFe 0.85 Mn 0.15 alloy made by mechanical alloying shows the best hydrogen storage property with the valid hydrogen capacity up to 220?mL/g at 293?K and 4.0?MPa, and the P睠 T behavior is also improved. The XRD and EDX analyses also show that the phase of these alloys contains V, TiFe, γ TiMnx, TiFe 2 and α FeV. The composition of these phases affects significantly the hydrogen storage properties of

Shell and shrinking core kinetics model of Mg-based hydrogen storage alloys

The kinetics equation of the Mg-based hydrogen storage alloys (Mg-Ni-MO) was established by the shell and shrinking core model. The total coefficients of the kinetics equation of the hydrogen absorption and desorption process with shell diffusion as the controlling step were determined by semi-empirical and semi-theoretical methods, and the apparent activation energy of the hydrogen absorption process was obtained. The calculation results can well accord with the experimental data, and can well forecast the hydrogen storage capacity and absorption rate at different times. By using the kinetics equation, the effects of temperature and pressure on the hydrogen storage process can also be well understood. The kinetics equation is helpful for the design of the hydrogen storage container.

Effects of Mm(NiCoAlMn)_5 hydrogen storage alloy coated with Ni-Co-P alloy by electroless plating on electrochemical properties of hydride electrodes

The effect of chemical plating with Ni Co P alloy on the properties of MH electrodes is investigated. The results show that the efficiency of storage alloy and the activation of MH electrode have been improved by introducing 1.74% cobalt in the Ni Co P alloy coating. The initial discharge capacity is 208 mAh/g. The maximum discharge capacity gets to 298.5 mAh/g. At the same time the cycle life of MH electrodes is improved. The discharge capacity of MH electrodes coated with Ni Co P is 88% of the maximum discharge capacity after 300 cycles. Whereas the discharge capacity of bare alloy electrodes retains 62% of the maximum capacity after 300 cycles. An increment of discharge capacity is mainly due to the superposition of the oxidation current of Co as well as improved efficiency of microcurrent collection. The effect of Ni Co P alloy coating by electroless plating on the kinetic properties of hydride electrode has been systematically investigated by electrochemical techniques. The results indicate that the kinetic properties of MH electrodes, including exchange current density, limiting current density, have been improved markedly. This improvement of kinetic properties leads to the decrease of the overpotential of anodic and cathodic polarization.

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 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).

STUDY ON Ti Ni La HYDROGEN STORAGE ALLOY

In ordertoimprovethe dischargecapacity of Ti2 Ni hydrogen storage alloy, the phases and effecton the property for Ti Nialloy with alittle La( La contentisbetween 5 25 wt% and12 62 wt%) were investigated in this paper. It is found that La exists in the form ofLaNi5 ,thesecond phase,in Ti Nialloy when La> 8 wt% . LaNi5 phasecaneffectivelyim provethe activity property and discharge capacity of Ti Ni alloy. While the soluble Ti inmain phase Ti2 Niisadverseto hydrogen adsorption desorption cycle and itshould be dimin ished .

Effect of cerium content on microstructure and hydrogen storage performance of Ti_(24)Cr_(17.5)V_(50)Fe_(8.5)Ce_x(x=0-1.0) alloys

Effect of Ce addition on microstructure and hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex（x=0, 0.5at.%, 0.8at.% and 1.0at.%） alloys was studied by X-ray diffraction, scanning electron microscopy and P-C-isotherm measurements.The results indicated that Ce addition was a useful way to improve the flatness of the plateau and increase hydrogen storage capacity of Ti24Cr17.5V50Fe8.5 alloy.It was indicated that both homogenization of composition and increase of hydrogen diffusion coefficient were the main reasons for improving the hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex alloys.

Study on Nanocrystalline Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

A sort of rare earth Mg-based system hydrogen storage alloys with AB3-type was prepared by double-roller rapid quenching method. The alloys were nanocrystalline multi-phase structures composed of LaNi3 phase and LaNi5 phase by X-ray diffraction and scanning electron microscopy analyses, and the suitable absorption/desorption plateau was revealed by the measurement of P-C-I curve. Electrochemical studies indicate that the alloys exhibit good electrochemical properties such as high capacity and stable cycle life, and the discharge capacity is 369 mAh·g-1 at 0.2 C (72 mA·g-1). after 460 cycles, the capacity decay was only 19.4% at 2 C (720 mA·g-1).

Effects of Pd substitution for Ni on corrosion performances of Mg_(0.9)Ti_(0.1)Ni_(1-x)Pd_x hydrogen storage alloys

The Mg0.9Ti0.1Ni1?xPdx (x= 0, 0.05, 0.1, 0.15) hydrogen storage electrode alloys were prepared by mechanical alloying. The main phases of the alloys were determined as amorphous by X-ray diffraction(XRD). The corrosion potentials of the alloys were measured by open circuit potential measurements and the values are ?0.478, ?0.473, ?0.473 and ?0.471 V (vs Hg/HgO electrode) for x=0, 0.05, 0.1, 0.15, respectively. The corrosion currents of the studied alloys were obtained by non-linear fitting of the anodic polarization curve using Bulter-Volmer equation and Levenberg-Marquardt algorithm, which were obtained after different cycles. The initial corrosion currents of the alloys are decreased with the increasing of Pd content. The increasing of Pd content in the alloys inhibits the corrosion rates of the electrode alloys with the progress of cycle number. The electrochemical impedance spectroscopy(EIS) was conducted after open circuit potential of the alloys stabilizing. The impedance data fit well with the theoretical values obtained by the proposed equivalent circuit model. The corrosion resistances and the thickness of surface passive film of the alloys, which were deduced by the analyses of EIS, are enhanced with the increasing of Pd content in the alloys, which are consistent with the results of corrosion rates obtained from anodic polarization measurements.