Hydrogenation and electrochemical studies of La–Mg–Ni alloys

La–Mg–Ni alloys are potential candidates for hydrogen storage materials. In this study, mechanical alloying with subsequent annealing under an argon atmosphere at 973 K for 0.5 h, were used to produce La_2-xMg_xNi₇ alloys (x = 0, 0.25, 0.5, 0.75, 1). Shaker type ball mill was used. An objective of the present study was to investigate an influence of amount of Mg in alloy on electrochemical, hydrogenation and dehydrogenation properties of La–Mg–Ni materials. X-ray diffraction analyses revealed formation of material with multi-phase structure. Obtained materials were studied by a conventional Sievert's type device at 303 K. It was observed that electrochemical discharge capacity and gaseous hydrogen storage capacity of La–Mg–Ni alloys increases with Mg content to reach maximum for La_1.5Mg_0.5Ni₇ alloy. Moreover, all of La–Mg–Ni alloys were characterized by improved hydrogen sorption kinetics in comparison to La–Ni alloy.     

In-situ formation of ultrafine MgNi3B2 and TiB2 nanoparticles: Heterogeneous nucleating and grain coarsening retardant agents for magnesium borate in Li–Mg–B–H reactive hydride composite

Li–Mg–B–H reactive hydride composite (RHC) has attracted extensive attention over the past decades for its extremely high hydrogen storage capacity (11.5 wt%). But the sluggish desorption kinetics for the second step dehydrogenation reaction need to be further improved. Herein, short rod-like TMTiO₃ (TM = Co, Ni) bimetallic oxides, which contain two kinds of transition metal elements, were synthesized and introduced into Li–Mg–B–H RHC for the first time. The NiTiO₃ exhibits excellent catalytic effect on the hydrogen desorption kinetic performance of Li–Mg–B–H RHC, and the incubation period for the second step dehydrogenation reaction is eliminated completely by reducing the apparent activation energy for the generation of MgB₂ from 296 kJ/mol to 269 kJ/mol. The NiTiO₃ doped Li–Mg–B–H RHC can desorb about 9.0 wt% H₂ without obvious attenuation of kinetic performance in five cycles. Mechanism analyses reveal that the in-situ generated nano-sized MgNi₃B₂ and TiB₂ species (∼5 nm) both meet the critical value ( < 10%) of the edge-to-edge matching model (5.77% for MgNi₃B₂ and 2.22% for TiB₂), which play a significant role in supporting the nucleation of MgB₂. Meanwhile, the extremely fine MgNi₃B₂ and TiB₂ heterogeneous nucleation sites can inhibit the excessive growth for a single crystal nucleus of MgB₂. The heterogeneous nucleation and grain refinement mechanisms caused by the novel bimetallic oxide could provide alternative insights into designing an in-situ generated nano-sized catalytic hydrogen storage system with enhanced kinetics and cyclic stability for hydrogen-fueled applications.     

High-performance La–Mg–Ni-based alloys prepared with low cost raw materials

La–Mg–Ni-based hydrogen storage alloys showed good application prospects owing to their high hydrogen storage capacity. However, the poor cycling stability was a key problem. In order to improve the cycling stability, low cost YFe_0.85 master alloy was used as raw material to prepare La–Mg–Ni-based La_0.8-xY_xMg_0.2Ni_3-0.85xFe_0.85x (x = 0.50, 0.55, 0.60) hydrogen storage alloys by powder sintering method. The alloys were mainly composed of PuNi₃ phase and MgCu₄Sn phase. With the increase of Y and Fe, the cell parameters of PuNi₃ phase decreased. Lower mismatch coefficient promoted the cycling stability. As the case of x = 0.60, the capacity retention rate rose up to 95.45%. Aside from the cycling stability, appropriate substitution content contributed to higher capacity and satisfactory kinetics. As the case of x = 0.55, the hydrogen storage capacity reached 1.529 wt%, and hydriding time for the x = 0.60 alloy shrank to 76.7% of that for alloys without Y and Fe at 303 K.     

An approach to design single BCC Mg-containing high entropy alloys for hydrogen storage applications

Mg is a lightweight element that can increase the gravimetric hydrogen storage capacity of high entropy alloys (HEAs). This work presents a new approach to design single-phase Mg-containing HEAs with attractive hydrogen storage properties. The design method is based on four calculated parameters (?, VEC, $\overline{\Delta {\text{H}}_{\infty }}$ and $\overline{\Delta {\text{H}}_{\text{f}}^{\text{o}}}$) that allow us to find alloy compositions that form single body-centered cubic (BCC) solid solutions with high hydrogen affinity. The method was tested in the Mg–Al–Ti–Mn–Nb system and the Mg₁₂Al₁₁Ti₃₃Mn₁₁Nb₃₃ alloy was selected among 1326 calculated compositions. This alloy was produced by high energy ball milling resulting in a homogeneous single-phase BCC alloy that absorbed 1.7 wt.% of H by forming a BCC monohydride. Despite its H uptake being H/M = 1, the gravimetric capacity of the lightweight Mg₁₂Al₁₁Ti₃₃Mn₁₁Nb₃₃ alloy was comparable to refractory BCC-HEAs with H uptake of H/M = 2.     

Effect of oxygen on the microstructure and hydrogen storage properties of V–Ti–Cr–Fe quaternary solid solutions

The effect of low (<300 ppm O) and high (10,000 ppm O) residual oxygen concentration in vanadium raw metals on the microstructure and hydrogenation properties of V₄₀Fe₈Ti₂₆Cr₂₆, was investigated by means of XRD, SEM, TEM and pressure-composition isotherms. A high oxygen concentration in the vanadium raw metal led to the formation of an oxygen-rich secondary phase isostructural with α-Ti. The lattice parameter of the BCC main phase of the high-oxygen sample was reduced to 3.0141 (3) Å compared to 3.0308 (2) Å for the low-oxygen sample. As a result of the high oxygen content the equilibrium hydrogen pressure of the material was increased from 1 MPa to 4 MPa. Deoxidization through the addition of 1 at% rare earth metal could be achieved. The lattice constant of the deoxidized sample was 3.0297 (3) Å, and the thermodynamic properties were also the same as in case of the low-oxygen sample.     

Effects of graphite addition and air exposure on ball-milled Mg–Al alloys for hydrogen storage

Magnesium hydride (MgH₂) is a promising candidate as a hydrogen storage material. However, its hydrogenation kinetics and thermodynamic stability still have room for improvement. Alloying Mg with Al has been shown to reduce the heat of hydrogenation and improve air resistance, whereas graphite helps accelerating hydrogenation kinetics in pure Mg. In this study, the effects of simultaneous Al alloying and graphite addition on the kinetics and air-exposure resistance were investigated on the Mg₆₀Al₄₀ system. The alloys were pulverized through high-energy ball milling (hereinafter HEBM). We tested different conditions of milling energy, added graphite contents, and air exposure times. Structural characterization was conducted via X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). H₂ absorption and desorption properties were obtained through volumetry in a Sieverts-type apparatus and Differential Scanning Calorimetry (DSC). The desorption activation energies were calculated using DSC curves through Kissinger analysis. Mg₆₀Al₄₀ with 10 wt% graphite addition showed fast activation kinetics, even after 2 years of air exposure. Graphite addition provided a catalytic effect on ball-milled Mg–Al alloys by improving both absorption and desorption kinetics and lowering the activation energy for desorption from 189 kJ/mol to 134 kJ/mol. The fast kinetics, reduced heat of reaction, and improved air resistance of these materials make them interesting candidates for potential application in hydride-based hydrogen storage tanks.     

Study of cyclic performance of V-Ti-Cr alloys employed for hydrogen compressor

The development of a suitable hydrogen compressor plays one of the key roles to realize the fuel cell vehicle as well as for many other stationary and mobile applications of hydrogen. V-Ti-Cr BCC alloys are considered as promising candidates for effective hydrogen storage. The cyclic durability of hydrogen absorption and desorption is very important for these alloys to be realized as practical options. In connection to this, two alloys of V-Ti-Cr, (1) V₄₀Ti_21.5Cr_38.5 and (2) V₂₀Ti₃₂Cr₄₈, were selected and their cyclic hydrogen absorption-desorption performance was evaluated up to 100 cycles for temperature and pressure ranges of 20–300 °C and 5–20 MPa, respectively. It has been found that the cyclic hydrogen storage capacity continuously decreased for one composition while it was stable after 10 cycles for another composition. This performance difference of the alloys was studied in terms of their structural and microscopic properties and the results are presented in this paper.     

The morphology and electrochemical properties of La1-xMgxNi3.4Al0.1 (x = 0.1–0.4) hydrogen storage alloys

In view of the importance of Mg in R-Mg-Ni-type alloys (R generally represents rare earth elements), the effect of Mg on the morphology and electrochemical performance of the as-cast La_1-xMg_xNi_3.4Al_0.1 (x = 0.1, 0.2, 0.3 and 0.4) hydrogen storage alloys were studied in this work. The samples possess multiphase structures, including Gd₂Co₇-, Ce₂Ni₇-, Pr₅Co₁₉-and CaCu₅-type, PuNi₃-and MgCu₄Sn-type phases. It is found that reasonably increasing Mg contents can promote the formation of Gd₂Co₇-and Ce₂Ni₇-type phase as well as Mg contents have important effects on phase morphology. Furthermore, fine-dispersed LaNi₅ structure in (La, Mg)₂Ni₇ matrix is beneficial to facilitate the hydrogen diffusion and exert the electrochemical properties for the alloys.The EIS results indicate that the charge transfer resistance decreases nonlinearly with increase of (La, Mg)₂Ni₇ phase content and presents approximately linear relationship with LaNi₅ phase content. When x equals to 0.2, the alloy displays more optimal comprehensive electrochemical properties, i.e. the discharge capacity reaches 357.4 mA/g, the high rate dischargeability at 1200 mA/g 60.1% and the cycling performance 74.5%.     

Enhanced thermal diffusivity and dehydrogenation of 2LiNH2MgH2 by doping with super activated carbon

Doping with the additives in metal-N–H system has been regarded as one of the most effective approaches to improve its hydrogen storage properties. Herein, we prepared super activated carbon (SuperC) through the activation of commercial activated carbon by KOH and evaluated its effect on dehydrogenation properties of 2LiNH₂MgH₂. Our studies show that doping with SuperC could effectively lower its dehydrogenation temperatures. For instance, 2LiNH₂MgH₂–10 wt% SuperC can release 4.86 wt% of hydrogen upon heating up to 300 °C with the onset and peak dehydrogenation temperatures of 71 °C and 168 °C, respectively. Moreover, the release of byproduct NH₃ was successfully suppressed. Measurement of thermal diffusivity suggests that the enhanced dehydrogenation properties may be ascribed to the improved heat transfer for solid-solid reaction resulting from doping with SuperC.     

Microstructure and hydrogen storage properties of (Ti0.32Cr0.43V0.25) + x wt% La (x = 0–10) alloys

The composite alloy of Ti_0.32Cr_0.43V_0.25 with x wt% La (where x = 0–10) was prepared by arc melting technique. The effect on hydrogen storage capacity, flatness of the plateau pressure, and residual hydrogen was investigated in La added Ti_0.32Cr_0.43V_0.25. Crystalline phase and microstructure of the prepared composite alloy were investigated and characterized by XRD, SEM and TEM. The crystal structure was refinement using Rietveld analysis. The effective hydrogen storage capacity of the composite alloy was found comparable to the parent alloy, when 5 wt% La was added. The effective hydrogen capacity (∼2.31 wt%) was close to that of the parent alloy (2.35 wt%) and the plateau slope was significantly improved from 30.5 of the parent alloy to 14.6. Appropriate mechanisms associated with the improved flatness by the La addition has been discussed in terms of the refined crystalline structure. Using TG/DTA method we have shown the differences in the interaction of residual hydrogen with the BCC phase of both parent alloy and 5 wt % La mixed alloy.     

On the long-term cyclic stability of near-eutectic Mg–Mg2Ni alloys

In this investigation, we report the cyclic performance, microstructure and thermal properties of near eutectic Mg–Ni alloys with different Ni contents (4.4, 11.3 and 16.3 at%). The starting cast ingots are mechanically chipped to flakes of about 400 μm, all displaying composite structures characterized by a typical eutectic microstructure with rather coarse features (1–5 μm). The flakes are cycled 1000 times at 330 °C under 30/1 bar H₂ for the absorption/desorption processes. The hydrogen storage capacity is maintained throughout the cycling: 5.09, 4.46 and 3.49 wt% H₂ for Ni16.3, Ni11.3 and Ni4.4 (at%), respectively. No significant microstructural change is observed, indicating the excellent stability of the alloys at elevated temperatures. Nevertheless, a marked porosity, and spheroidal Mg₂Ni clusters can be noted after cycling, however their exact contribution to reaction kinetics has yet to be fully elucidated. An attempt is made to estimate the dehydrogenation activation energy of Ni16.3, and the calculated value seems comparable to that obtained for an early cycling stage (10 cycles). In the light of the superior stability under cyclic service and the low decomposition temperature, the Mg–Mg₂Ni system is shown to possess an excellent potential for long-term hydrogen and heat storage applications.     

Elaboration and electrochemical characterization of Mg–Ni hydrogen storage alloy electrodes for Ni/MH batteries

Mg–Ni hydrogen storage alloy electrodes with composition of Mg–33, 50, 67 Ni at. % in amorphous phase were prepared by means of mechanical alloying (MA) process using a planetary ball mill. The electrochemical hydrogen storage characteristics and mechanisms of these electrodes were investigated by electrochemical measurements, X–ray diffraction (XRD) and scanning electron microscope (SEM) analyses. The relationship between alloy composition and electrochemical properties was evaluated. In addition, optimum milling time and composition of Mg–Ni hydrogen storage alloy with acceptable electrochemical performance were determined. XRD results show that the alloys exhibit dominatingly amorphous structures after milling of 20 h. The electrochemical measurements revealed that the discharge capacity of Mg₃₃Ni₆₇ and Mg₆₇Ni₃₃ alloy electrodes reached a maximum when alloys were prepared after 20 h of milling time (260 and 381 mAhg^?1, respectively). The maximum discharge capacity of Mg₅₀Ni₅₀ alloy was observable after 40 h milling (525 mAhg^?1). It was also found that the cyclic stability of the alloys increased with increasing Ni content. Among these alloys, the amorphous Mg₅₀Ni₅₀ alloy presents the best overall electrochemical performance. In this paper, electrode process kinetics of Mg₅₀Ni₅₀ alloy electrode was also studied by means of electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The impedance spectra of electrodes were measured at different depths of discharge (DODs). The observed spectra were fit well with the equivalent circuit model used in the paper. The electrochemical parameters calculated from electrochemical impedance were also compared. The electrochemical discharge and cyclic performance of 20, 40 and 60 h milled Mg₅₀Ni₅₀ alloy electrodes were demonstrated by the fitted charge transfer resistance and Warburg impedance obtained at various DODs. It was further observed that the controlling-step of the discharge process changed from a mixed rate-determining process at lower DODs to a mass-transfer controlled process at higher DODs. The fitted results demonstrated that charge–transfer resistance (R_ct) increased with DOD. The R_ct of 40 h milled Mg₅₀Ni₅₀ alloy (29.27 Ω) was lower than that of 20 h (41.89 Ω) and 60 h milled alloys (92.43 Ω) at fully discharge state.