Structure and electrochemical properties of the Fe substituted Ti–V-based hydrogen storage alloys

To elucidate the effects of Fe on the Ti–V-based hydrogen storage electrode alloys, the Ti_0.8Zr_0.2V_2.7−xMn_0.5Cr_0.8Ni_1.0Fe_x (x = 0.0–0.5) alloys were prepared and their structures and electrochemical properties were systematically investigated. XRD results show that all the alloys consist of a C14 Laves phase with hexagonal structure and a V-based solid solution phase with bcc structure. With increasing Fe content, the abundance of the C14 Laves phase gradually decreases from 43.4 wt% (x = 0.0) to 28.5 wt% (x = 0.5), on the contrary, that of the V-based solid solution phase monotonously increases from 56.6 wt% to 71.5 wt%. In addition, SEM observation finds that the grain size of the V-based solid solution phase is first gradually reduced and then enlarged with increasing x. Electrochemical investigations indicate that the substitution of Fe for V markedly improves the cycling stability and the high rate dischargeability of the alloy electrodes, but decreases the maximum discharge capacity and the activation performance. Further electrochemical impedance spectra, the linear polarization curve and the potentiostatic step discharge measurements reveal that the electrochemical kinetics of the alloy electrodes should be jointly controlled by the charge-transfer reaction rate on the alloy surface and the hydrogen diffusion rate in the bulk of the alloys. For the alloy electrodes with the lower Fe content (x = 0.0–0.2), the hydrogen diffusion in the bulk of the alloys should be the rate-determining step of its discharge process, and while x increases from 0.3 to 0.5, the charge-transfer reaction on the alloy surface becomes to the rate-determining step, which induces that the electrochemical kinetics of the alloy electrodes is firstly improved and then decreased with increasing Fe content.     

Hydrogen evolution from cathodically charged titanium aluminide alloy Ti–24Al–11Nb

A Ti₃Al-based titanium aluminide alloy, Ti–24Al–11Nb, was cathodically charged with hydrogen in a 5% H₂SO₄ aqueous solution for various charging times, and the formation and dissociation of the hydride, the hydrogen evolution behavior and the total hydrogen uptake were investigated mainly by means of X-ray diffractometry and thermal desorption spectroscopy (TDS). The same kind of hydride phase as observed previously in Ti–25Al alloy (hexagonal hydride) was presumably formed in the Ti–24Al–11Nb alloy after cathodic charging. No damage, such as cracks, was induced by hydrogen charging. Two kinds of TDS peaks, one probably corresponding to hydride dissociation and the other to hydrogen dissolution in the normal lattice site, were found after longer hydrogen charging. It is suggested that niobium addition to Ti₃Al-based titanium aluminide alloy may reduce hydrogen susceptibility during cathodic charging.     

XRD study of the hydrogenation and dehydrogenation process of the two different phase components in a Ti–V-based multiphase hydrogen storage electrode alloy

Hydrogenation and dehydrogenation of two different phases in a multiphase Ti–V-based alloy Ti_0.8Zr_0.2V_1.867Mn_0.373Cr_0.56Ni_0.7, namely the C14 Laves phase with hexagonal structure and the V-based solid solution phase with body centered cubic (bcc) structure during electrochemical charging and discharging were investigated by X-ray powder diffraction (XRD) analysis. For the alloy investigated, the C14 Laves phase component, which had good surface electrochemical activity for decomposing water, was hydrogenated from the very beginning of the charging process and was providing hydrogen to both phase components throughout the entire electrochemical charging process. The V-based solid solution phase, which had no or very low surface electrochemical activity for decomposing water during electrochemical charging, could obtain hydrogen only from its neighboring C14 Laves phase component when the hydrogen content of which was high enough to build up an adequate pressure to feed hydrogen to its neighboring phase component. The V-based solid solution phase experienced a phase change when the hydrogen in it reached a definite level, namely from bcc to body centered tetragonal (bct) structure. Probably due to the high stability of bct hydride phase of the V-based solid solution phase, it did not revert back to the initial bcc structure during the electrochemical discharging process conducted in our experiment at the room temperature and atmospheric pressure.     

Observation of hydrogen absorption/desorption reaction processes in Li–Mg–N–H system by in-situ X-ray diffractmetry

The in-situ XRD measurements on dehydrogenation/rehydrogenation of the Li–Mg–N–H system were performed in this work. The ballmilled mixture of 8LiH and 3Mg(NH₂)₂ as a hydrogenated phase gradually changed into Li₂NH as a dehydrogenated phase during heat-treatment at 200 °C in vacuum for 50 h. Neither Mg-related phases nor other intermediate phases were recognized in the dehydrogenated phase. With respect to the hydrogenation process, the dehydrogenated state gradually returned to the mixed phase of the LiH and Mg(NH₂)₂ without appearance of any intermediate phases during heat treatment at 200 °C under 5 MPa H₂ for 37 h and during slow cooling down to room temperature through 24 h. In the hydrogenation process at 200 °C under 1 MPa H₂, however, the growing up of the LiNH₂ and LiH phase was observed in the XRD profiles before the 3Mg(NH₂)₂ and 8LiH phases were formed as the final hydrogenated state. This indicates that the LiNH₂ and LiH phase essentially appears as an intermediate state in the Li–Mg–N–H system composed of 3Mg(NH₂)₂ and 8LiH.     

Effects of B, Fe, Gd, Mg, and C on the structure, hydrogen storage, and electrochemical properties of vanadium-free AB2 metal hydride alloy

The structural, gaseous phase hydrogen storage, and electrochemical properties of a series of vanadium-free AB₂ Laves phase based metal hydride alloys with various modifiers (Ti₅Zr₃₀Cr₉Mn₁₉Co₅Ni_32−xM_x, M = B, Fe, Gd, Mg, and C) were studied. While B and Fe completely dissolve in the main AB₂ phases, Gd, Mg, and C form individual secondary phases. The solubilities of Gd, Mg, and C in the AB₂ phases are not detectable, 0.3 at.%, and very low, respectively. The C14 crystallite sizes, C15 phase abundances, and Zr₇Ni₁₀ phase abundances of modified alloys are larger than those of the base alloy. All modified alloys show decreases in plateau pressure, reversible gaseous phase storage capacity, formation activity, electrochemical capacity, and cycle life. A small amount of boron (0.2 at.%) and carbon in the alloy improve the half-cell high-rate dischargeability and bulk hydrogen diffusion. All modifiers, except for boron, reduce the surface exchange reaction current densities of the alloys. Both Mg and C show improvement in charge retention. Full-cell high-rate performance is improved by adding only a small amount of boron (0.2 at.%). Fe, Gd and 0.2 at.% of boron improve the low-temperature performance of the sealed batteries.     

Formation of a tetragonal phase hydride in Ti–Mo–H system

The structural relationship between the hydride phases in Ti–Mo–H solid solution system (Mo content up to 15 at% in the alloy) during dehydrogenation process under annealing has been studied by conventional and in situ X-ray powder diffraction and transmission electron microscopy (TEM) analysis. During dehydrogenation, the saturated hydrides of the Ti–Mo alloys with fcc δ-phase structure transfer into bcc β-phase at higher temperatures. An associated hydrogen concentration reduction for the δ-phase hydride is observed in the process. However, as the hydrogen concentrations decrease to certain values (H/M  1.1–1.7), the unsaturated δ-phase formed at high temperature would become unstable at lower temperature, and transfer into a tetragonal phase (denoted the -phase here). Unlike that of the -phase in Ti–H system, the phase transition does not occur for the saturated δ-phase with hydrogen concentration close to the stoichiometric limit. The hydrogen concentration of this -phase hydride is in between that of the tetragonal γ and -phase in Ti–H system, but more close to the γ-phase. The occurrence region of this -phase expands along with the increase of the Mo content in the alloys. The phase has a lattice similar to that of the -phase in Ti–H system with corresponding fct unit-cell c/a < 1.     

Influence of the rare earth composition on the properties of Ni–MH electrodes

Lattice parameters, hydrogen absorption properties and electrochemical cycling properties up to 240 cycles have been measured as a function of the Ce content for alloys of composition La_0.82−xCe_xNd_0.15Pr_0.03Ni_3.55Mn_0.4Al_0.3Co_0.75 (0≤x≤0.82). The results show the strong increase of the plateau pressure correlated to the cell volume decrease as a function of x. On the other hand, the hydrogen capacity measured in solid–gas reaction as well as the electrochemical capacity decreases slightly. The results show that both La and Ce have to be present to achieve a good cycle life, the cycling degradation being almost independent of their relative quantities in a broad range of concentrations.     

TiCrV hydrogen storage alloy studied by positron annihilation spectroscopy

We have studied the structural changes of Ti₂₄Cr₃₆V₄₀ alloy prepared by arc-melting using positron annihilation spectroscopy and X-ray diffraction (XRD) as functions of the number of hydrogen pressure swing cycles and degassing temperature. As the hydrogen storage capacity decreased with the number of pressure swing cycles, both positron lifetime and XRD peak width increased. Upon hydriding, the crystal structure changed from bcc to bct with increased lattice constants. The increase in positron lifetime is due to the volume expansion caused by hydride formation. After degassing at 500 °C, the hydrogen storage capacity recovered to 95% of the initial level, and the XRD peak width and the lattice constants nearly completely returned to their initial values. However, the positron lifetime was still longer than the initial level suggesting the survival of dislocations. The degradation of hydrogen storage capacity is probably caused by both hydride formation and the generation of dislocations.     

La–Mg–Ni ternary hydrogen storage alloys with Ce2Ni7-type and Gd2Co7-type structure as negative electrodes for Ni/Mh batteries

Hydrogen strorage alloys with formula La_1.5Mg_0.5Ni₇ were prepared by induction melting followed by different annealing treatments (1073, 1123 and 1173 K) for 24 h. The alloy composition, alloy microstructure and electrochemical properties were investigated, respectively. The results showed that the multi-phase structure of as-cast alloy was converted into a double-phase structure (Gd₂Co₇-type phase and Ce₂Ni₇-type phase) through annealing treatments. Mg atoms were mainly located in Laves unit of Gd₂Co₇-type unit cell and Ce₂Ni₇-type unit cell. The electrochemical capacity of alloy electrodes after annealing treatment could be up to 390 mAh/g. The cyclic stability of alloy electrodes was significantly improved by annealing treatments; After 150 charge/discharge cycles, the capacity retention ratio of alloy annealed at 1173 K was the highest (81.9%). The high rate dischargeability of alloy electrodes was also improved due to annealing treatment.     

Improvement of the hydrogen storage properties and electrochemical characteristics of Ti0.85VFe0.15 alloy by Ce substitution

The effect of Ce substitution for Ti on the microstructure, hydrogen absorption characteristics and electrochemical properties of Ti_0.85−xCe_xVFe_0.15 (x = 0, 0.02 and 0.05) is studied in detail. In the Ti-V-Fe series, the composition Ti_0.85VFe_0.15 which crystallizes in single phase BCC structure shows the highest hydrogen storage capacity of 3.7 wt%. In the present study, the effect of Ce addition (2 and 5 at%) on the hydrogen absorption properties of Ti_0.85VFe_0.15 has been investigated by X-ray diffraction, electron probe microanalysis (EPMA) and pressure-composition isotherm studies. The hydrogen absorption capacity is found to be higher for the Ce substituted alloys. The alloys Ti_0.85VFe_0.15, Ti_0.83Ce_0.02VFe_0.15 and Ti_0.80Ce_0.05VFe_0.15 show maximum hydrogen storage capacities of 3.7, 4.02 and 3.92 wt%, respectively. Kinetic studies show that the hydrogen absorption is quite fast for all the three alloys and they reach near saturation value in about 120 s. Electrochemical studies of the Ce (2 at%) substituted alloy, Ti_0.83Ce_0.02VFe_0.15 show higher electrocatalytic activity for the hydrogen electrode reactions as compared to Ce-free parent compound, Ti_0.85VFe_0.15.     

Changes in the microstructure and hydrogen storage properties of Ti-Cr-V alloys by ball milling and heat treatment

Changes in the microstructure and hydrogen storage properties of Ti-Cr-V alloys were investigated after a combination of ball milling and heat treatment. Two different sets of balls and vials made of tungsten carbide (WC) and stainless steel (STS) were used for milling the samples. Ball milling using WC balls and vials induced WC contamination, and it caused compositional changes in the matrix during heat treatment. When STS balls and vials were used, meanwhile, no peak of the second phase caused by contamination was found in the X-ray diffraction (XRD) data. In the case of the sample that completed only the milling process, the crystallite size calculated from the XRD data, 20-30 nm, agreed well with the grain size obtained from transmission electron microscopy (TEM). On the other hand, for the sample that was heat treated after milling, the strain decreased from 0.74% to 0.18%, the crystallite size increased to 70-80 nm, and the grain size grew up to the level of hundreds of nanometers. The changes in microstructure induced by the ball milling and heat treatment influenced the hydrogen storage properties, such as plateau pressure, hysteresis, and phase transformation with hydrogen absorption. Thus, the relationship between the microstructure and hydrogen storage properties can be explained.     

Effects of rapid solidification on the phase structures and electrochemical properties of a V3TiNi0.56Co0.14Nb0.047Ta0.047 alloy

The crystal structures and electrochemical properties of a V₃TiNi_0.56Co_0.14Nb_0.047Ta_0.047 alloy prepared by the melt-spinning method were studied. The rapidly solidified alloy consists of a major Vanadium-based solid solution phase and a secondary Ti₂Ni-based phase. The secondary phase exists between the dendritic arms of the major phase, showing a typical eutectic characteristic. With increasing cooling rate, the amount of the secondary phase decreases but the lattice parameters of both the major phase and the secondary phase show no obvious change. Because the disappearance of the catalytic effect of the secondary phase, the rapidly solidified alloy shows bad electrochemical properties except cycle stability.     

Cobalt-free over-stoichiometric Laves phase alloys for Ni–MH batteries

The charge–discharge cycling behavior of the over-stoichiometric Laves phase alloy Zr_0.75Ti_0.25V_0.9Mn_0.4Cr_0.3Ni_1.4 as hydride electrode has been studied in a negative electrode-limited sealed cell. This cobalt-free alloy shows a maximum discharge capacity C_max=373 mAh g⁻¹ at 160 mA g⁻¹ discharge current and a high rate dischargeability of 285 mAh g⁻¹ at 1500 mA g⁻¹ discharge rate. After 600 cycles the discharge capacity is 81% of the C_max; the alloy also shows good charging efficiency (98%) and low temperature discharge rate.     

Effects of Mo additive on the structure and electrochemical properties of low-temperature AB5 metal hydride alloys

After an annealing treatment at 960 °C for 8 h, the molybdenum added into previously designed AB₅ alloys for −30 °C applications segregates into spheres with diameters between 1 and 10 μm. A secondary phase with Zr-to-other elements ratio of about 1-to-5, over- (AB₇), and under-stoichiometric (AB₄) phases were observed in most of the alloys regardless of Mo-content. As the Mo-content increases, the AB₇ phase disappears while the AB₄ phase grows in size and abundance. Regarding the gaseous absorption properties, a small amount of Mo (0.2 at.%) in the main phase reduces the plateau pressure and hydride heat of formation uniformly for all Mo-containing alloys. The reduction in main phase abundance causes a decrease in both the total and the reversible hydrogen storage capacities. In electrochemical testing, the addition of Mo decreases the discharge capacity, high-rate dischargeability, and hydrogen diffusion in the bulk. The influence of Mo-addition to general battery performance is very minor. However, the low-temperature AC impedance measured at −40 °C shows reduced charge transfer resistance and increased double layer capacitance in the Mo-containing alloys. Mo was found to assist the surface reaction at very low temperatures, and the effect is proportional to the amount of addition as noted by the increasing surface area and catalytic ability, which is similar to the case of AB₂ alloys.     

Synthesis of NaAlH4-based hydrogen storage material using milling under low pressure hydrogen atmosphere

The present study highlights the advantages of milling NaH/Al under moderate hydrogen pressure as a favourable production step for NaAlH₄-based hydrogen storage materials. Firstly, it is demonstrated that NaAlH₄ can be obtained by applying a moderate hydrogen pressure (6–12 bar) during milling of NaH and Al with and without the presence of an inexpensive catalyst (TiCl₄). The yield of NaAlH₄ depends critically on process parameters, such as hydrogen pressure and milling time. A fully converted product is capable of reversible hydrogen storage without any activation procedure. Under optimized conditions, a capacity of 4.2 wt.% was achieved and kinetics in the first desorption are comparable to NaAlH₄ doped with TiCl₃. Secondly, the synthesis has been optimized towards shorter milling times. By applying a few absorption/desorption cycles to material that was partially converted during milling, almost full reversible storage capacity can be reached. In addition, kinetics is extremely enhanced. For example, such material exhibits an optimum capacity already after two sorption cycles at 100 bar and 125 °C and allows to absorb 80% of the reversible hydrogen content within a few minutes.     

Improving the performance of hydrogen storage electrodes based on mechanically alloyed Mg61Ni30Y9

Amorphous Mg₆₁Ni₃₀Y₉ powder was produced by mechanical alloying using a Retsch planetary ball mill under liquid nitrogen cooling. Additional gentle milling with graphite powder resulted in a thin graphite coating of powder particles. Further milling with a high energy SPEX mill transferred the alloy into a fully nanocrystalline state. The morphological and microstructural changes were followed by means of XRD, SEM, TEM and DSC. Hydrogen storage electrodes based on those alloy powders were fabricated and their cathodic and anodic polarization behaviour and their charge–discharge cycling behaviour in 6 M KOH solution were investigated. It was found that the alloy modification from a non-defective amorphous to a highly defective nanocrystalline state is more effective for improving the hydrogen sorption properties of the alloy than the graphite coating, but is detrimental for the alloy passivation. Accordingly, a SPEX-milled powder electrode exhibits with C_max = 570 mAh/g a higher maximum discharge capacity than a coated Retsch-milled powder electrode with C_max = 435 mAh/g, but degrades faster during repeated cycling. Using graphite powder supporting material for electrode preparation on a nickel foam carrier was found to be much more beneficial than nickel powder for achieving maximum discharge performance.     

The effect of Nd content on the electrochemical properties of low-Co La–Mg–Ni-based hydrogen storage alloys

The low-Co content La_0.80−xNd_xMg_0.20Ni_3.20Co_0.20Al_0.20 (x = 0.20, 0.30, 0.40, 0.50, 0.60) alloys were prepared by inductive melting and the effect of Nd content on the electrochemical properties was investigated. XRD shows that the alloys consist mainly of LaNi₅ phase, La₂Ni₇ phase and minor LaNi₃ phase. The electrochemical P–C–T test shows hydrogen storage capacity increases first and then decreases with increasing x, which is also testified by the electrochemical measurement that the maximum discharge capacity increases from 290 mAh/g (x = 0.20) to 374 mAh/g (x = 0.30), and then decreases to 338 mAh/g (x = 0.60). The electrochemical kinetics test shows exchange current density I₀ increases with x increasing from 0.20 to 0.50 followed by a decrease for x = 0.60, and hydrogen diffusion coefficient D increases with increasing x. Accordingly high rate dischargeability increases with a slight decrease at x = 0.60 and the low temperature dischargeability increases with increase in Nd content. When x is 0.50, the alloy exhibits a better cycling stability.     

Hydrogen solution properties in a series of amorphous Zr–Hf–Ni alloys at elevated temperatures

Amorphous alloys are anticipated as new membrane materials for high purity hydrogen production, as substitutes for expensive palladium alloys. For amorphous Zr–Ni-based alloys reported to date, hydrogen permeability increases with Zr content. Hydrogen solution properties in a series of amorphous Zr–Hf–Ni ternary alloys were measured carefully using the Sieverts method and residual hydrogen measurements to investigate the reason. Results indicate that hydrogen solubility in the ternary alloys increases with increasing Zr to improve hydrogen permeability, not because of the geometrical atomic structure but because of higher hydrogen affinity of Zr than that of Hf. Increased permeability with Zr in other amorphous Zr–Ni-based alloys is also expected to be attributable to the same reason. Additionally, hydrogen was found with low mobility, and was not removable even after 10 h evacuation at 573 K; the importance of decreasing low mobility hydrogen as a countermeasure against hydrogen embrittlement was pointed out. Equilibrium hydrogen concentration was found not to obey Sieverts’ law with respect to hydrogen pressure. Rather, it was linear roughly to the quarter power. Parameters to reproduce pressure–composition isotherms were determined using Kirchheim's theory.     

Preparation and electrochemical study of cerium–silica sol–gel thin films

Design and development of suitable multilayered systems for delaying corrosion advance in metals requires that both the alteration mechanisms of the metal and the behaviour and properties of the protective coatings be known. Coatings prepared by the sol–gel method provide a good approach as protective layers on metallic surfaces. This kind of coatings can be prepared from pure chemical reagents at room temperature and atmospheric pressure, with compositions in a very wide range of environmentally non-aggressive precursors. Sol–gel coatings based on siloxane bonded units were prepared starting from an organic–inorganic hybrid system. The precursors were γ-methacryloxypropyltrimethoxysilane (MAP) and tetramethoxysilane (TMOS). Cerium nitrate hexahydrate in three different concentrations was added. Cerium salts may perform a similar protective effect to that carried out by the well-known lead oxides and chromium salts, even though in this case a negative environmental impact is not expected. Application of coatings upon pure zinc substrates and common glass slides were performed by spinning. Coated samples were heat treated at 40 °C for 6 days. Optical measurements (UV-Vis absorption and diffuse reflectance spectroscopies) pointed out that the coatings were colourless and transparent, reducing the diffuse reflectance of the metallic surface up to 60%. Optical and scanning electron microscopies (SEM) allowed observation of the texture and microstructure of the coated samples, both before and after the corrosion tests were carried out. Likewise, the remaining sols were kept to gelify at 60 °C for 4 days and then powdered to obtain suitable samples for analysing them by other characterisation techniques (Fourier transformed infrared, FTIR and differential thermal analysis, DTA). Electrochemical measurements were performed by impedance spectroscopy. This technique was used to clarify the anticorrosive protection role of cerium ions incorporated into the hybrid sol–gel network. The effect of cerium concentration on the impedance spectra was analysed, as well as the system behaviour against the corrosive medium (0.6 M NaCl aqueous solutions), as a function of exposure time. From the electrochemical point of view, the sol–gel films behave as a conversion coating on the metallic surface.     

Structural and electrochemical properties of TixZr7−xNi10

Simple ternary alloys with formula Ti_xZr_7−xNi₁₀ (x between 0 and 2.5) were studied as a potential replacement for Laves phase alloys used in the negative electrodes of nickel metal hydride batteries. The samples were prepared by arc-melting and were not annealed. The samples retained a high degree of disorder, which contributed positively to activation and other electrochemical properties. Before hydrogenation, the alloys have a Zr₇Ni₁₀ orthorhombic structure mixed with some C15 and ZrO₂ secondary phases. The amount of C15 secondary phase is important to the bulk diffusion of hydrogen and the surface electrochemical kinetics. That is, the diffusion coefficient and the exchange current both increase in the presence of C15 secondary phase. The proportion of C15 secondary phase is controllable by stoichiometry design. For instance, a slightly higher Zr content reduces the C15 content. Further, as the titanium substitution level increases: (1) the lattice constants decrease; (2) the PCT plateau pressure increases; (3) activation becomes easier; and (4) the high rate dischargeability improves.