Investigation on kinetics mechanism of hydrogen absorption in the La2Mg17-based composites

A new model has been successfully used to investigate the hydrogen absorption kinetics mechanism of La₂Mg₁₇-based composites. The results indicate that different preparation conditions lead to different rate-controlling steps during hydrogen absorption process. For La₂Mg₁₇–LaNi₅ composite synthesized by the method of melting, the rate-controlling step is the surface penetration of hydrogen atoms, which does not change by addition agent (LaNi₅). However, mechanical milling can change the rate-limiting steps of hydriding reaction in the La₂Mg₁₇–LaNi₅ composite from surface penetration to diffusion of hydrogen in the hydride layer. With the enhancement of milling intensity, the rate-controlling step in La_1.8Ca_0.2Mg₁₄Ni₃ alloy changes from surface penetration to diffusion. In addition, the activation energies of hydrogen absorption for La₂Mg₁₇−20 wt%LaNi₅ and La_1.8Ca_0.2Mg₁₄Ni₃ are obtained by this model.     

Structural investigation and hydrogen storage properties of Ca3-xLaxMg2Ni13 alloys

The phase structures and hydrogen storage properties of the Ca_3-xLa_xMg₂Ni₁₃ alloys were investigated. It was found that the La substitution is unfavorable for the formation of the Ca₃Mg₂Ni₁₃-type phase. The La-substituted alloys consist of multiple phases. Increasing La content to x = 2.25 leads to a disappearance of Ca₃Mg₂Ni₁₃-type phase. Among these alloys, the Ca_1.5La_1.5Mg₂Ni₁₃ alloy has highest equilibrium pressures of hydrogen absorption–desorption and a highest hydrogen desorption capacity of 1.34 wt.% at 318 K. The discharge capacity decreases for La-substituted alloys. However, the cycling capacity retention rate (S₃₀) increases from 13.7 to 67.6% when x increases from 0 to 3.     

Properties of La0.2Y0.8Ni5−xMnx alloys for high-pressure hydrogen compressor

Hydrogen absorption/desorption properties of La_0.2Y_0.8Ni_5−xMn_x (x = 0.2, 0.3, 0.4) alloys for high-pressure hydrogen compression application were investigated systematically. The Pressure–Composition isotherms and absorption kinetics were measured at 293, 303 and 313 K by the volumetric method. XRD analyses showed that all the investigated alloys presented CaCu₅ type hexagonal structure and the unit cell volume increased in both a and c lattice axes with Mn substitution. Hydrogen absorption/desorption measurements revealed that Mn could lower the plateau pressure effectively, improve the hydrogen storage capacity and absorption kinetics but slightly increase the slope of the pressure plateau and hysteresis. The study results suggest that La_0.2Y_0.8Ni_4.8Mn_0.2 is suitable for the high-pressure stage compression of the hydrogen compressor and the other two alloys, La_0.2Y_0.8Ni_4.7Mn_0.3 and La_0.2Y_0.8Ni_4.6Mn_0.4, for the preliminary stage.     

Study on the eutectic formation and its correlation with the hydrogen storage properties of Mg98Ni2-xLax alloys

Transition metals and rare-earth elements have excellent catalytic effects on improving the de-/hydrogenation properties of Mg-based alloys. In this study, a small amount of La is used to substitute the Ni in Mg₉₈Ni₂ alloy, and some Mg₉₈Ni_2-xLa_x (x = 0, 0.33, 0.67, and 1) alloys show the better overall hydrogen storage properties. The effects of La on the solidification and de-/hydrogenation behaviors of the alloys are revealed. The results indicate that different factors dominate the processes of hydrogen absorption and desorption. The Mg₉₈Ni_1·67La_0.33 alloy absorb 7.04 wt % hydrogen at 300 °C, with the highest isothermal absorption rate, the Mg₉₈Ni_1·33La_0.67 hydride show the highest isothermal desorption rates and the lowest peak desorption temperature of 327 °C. The La addition can increase the driving force of hydrogenation, thus the hydrogenation rates and capacities of the Mg₉₈Ni_1·67La_0.33 and Mg₉₈Ni_1·33La_0.67 alloys are improved. The formation of refined eutectic structures is a key factor that facilitates the desorption processes of the Mg₉₈Ni_2-xLa_x hydrides with x = 0.67 and 1. High-density LaH₃ nanophses are in-situ formed from the LaMg_x (8.5 < x < 12) phase, which results in the improved de-/hydrogenation properties. The further La addition deteriorates the hydrogen storage properties of Mg₉₈Ni_2-xLa_x alloy.     

Hydrogen storage properties of flexible and porous La0.8Mg0.2Ni3.8/PVDF composite

A study on the hydrogen storage properties of flexible and porous La_0.8Mg_0.2Ni_3.8/PVDF (polyvinylidene fluoride) composite was reported. In this composite, PVDF acted as a binder to connect the alloy powders and (NH₄)₂CO₃ as a pore-forming agent to create void space. Increasing PVDF content, the hydrogen absorption kinetics of the composite gradually decreased. Increasing (NH₄)₂CO₃ from 1% to 5%, the capacity firstly increased and then decreased. 0.08–0.13 wt% increased capacity for the composite was observed at 70 °C by comparison with the intrinsic composite (La_0.8Mg_0.2Ni_3.8/1%PVDF). Varying temperature from 0 °C to 100 °C, 0.1–0.15 wt% increased capacity were obtained for the typical porous composite (La_0.8Mg_0.2Ni_3.8/1%PVDF/3%(NH₄)₂CO₃). The PVDF-assisted composite showed the flexible/solidified characteristic in hydriding/dehydriding, which maybe lowed down the oxidation of the alloy powders and preserved the void space. Finally, ∼0.1 wt% increased capacity remained after ten hydriding/dehydriding cycles.     

Hydrogen storage properties of Nb–Hf–Ni ternary alloys

The hydrogen storage properties of Nb_xHf_(1−x)/2Ni_(1−x)/2 (x = 15.6, 40) alloys were investigated with respect to their hydrogen absorption/desorption, thermodynamic, and dynamic characteristics. The PCT curves show that all the specimens can absorb hydrogen at 303 K, 373 K, 423 K, 473 K, 523 K, 573 K, and 673 K, but they couldn't desorb hydrogen below 373 K. The maximum hydrogen absorption capacity reaches 1.23 wt.% for Nb_15.6Hf_42.2Ni_42.2 and 1.48 wt.% for Nb₄₀Hf₃₀Ni₃₀ at 303 K at a pressure of 3 MPa. When the temperature was increased, the hydrogen absorption capacities significantly decreased. However, the hydrogen equilibrium pressure increased. When the temperature exceeded 523 K, the hydrogen equilibrium pressure disappeared. When niobium content was increased, the kinetic properties of hydrogen absorption/desorption improved. The results from the microstructure analysis show that both alloys consist of the BCC Nb-based solid solution phase, the B_f-HfNi intermetallic phase, and the eutectic phase {B_f-HfNi + BCC Nb-based solid solution}. When the Nb content was increased, the volume fraction and Nb content in the Nb-based solid solution phase increased. Thus, the improved kinetics is related to the increase in the primary BCC Nb-based solid solution in the Nb₄₀Hf₃₀Ni₃₀ alloy. The kinetic mechanisms of hydrogen absorption/desorption in these two alloys are found to obey the chemical reaction mechanism at all temperatures tested.     

Effect of La-content on the hydrogenation properties of the Ce1−xLaxNi3Cr2 (x=0.2, 0.4, 0.6, 0.8, 1) alloys

The effect of partial substitution of Ce by La in CeNi₃Cr₂ hydrogen storage alloy has been systematically investigated. All intermetallic compounds Ce_1-xLa_xNi₃Cr₂ (x = 0.2, 0.4, 0.6, 0.8, 1) synthesized by arc melting method are well characterized by the means of XRD and SEM. XRD results show that all the alloys are crystallized as a single-phase compound in the hexagonal CaCu₅ type structure. The substitution of Ce by La leads to increase the unit cell volume of the alloy. Hydrogen storage capacity has been investigated in the temperature and pressure range of 293 K ≤ T ≤ 323 K and 0.5 ≤ P ≤ 45 bar respectively using pressure-composition isotherm. The P-C isotherm curves show that the plateau pressure of the hydrogen absorption decreases and hydrogen storage capacity increases with increasing La content in the alloy. The enthalpy (?H) and entropy (?S) of dissolved hydrogen for all systems has been calculated using Van’t Hoff plot. The variation of ?H and ?S with hydrogen content has also been studied which confirm the phase boundaries.     

Comparative analysis of the hydriding kinetics of LaNi5, La0.8Nd0.2Ni5 and La0.7Ce0.3Ni5 compounds

In two-phase domains, the plateau pressure of hydride forming materials (such as intermetallic compounds or IMCs) depends markedly on the operating temperature (Van’t Hoff relationships). Therefore, for practical applications, it is necessary to select hydrogen storage materials by considering the thermal environment of the hydride tank. The thermodynamic properties (absorption and desorption pressure plateaux) of IMCs can be adjusted to some extend by chemical alloying with foreign metals and substitution on different crystallographic sites. In this paper, we report on the hydriding kinetics of substituted AB₅ compounds. Isotherms have been measured at different temperatures on La_xNd_1−xNi₅ (x ≈ 0.2) and La_xCe_1−xNi₅ (x ≈ 0.3) compounds. Pneumato-chemical impedance spectroscopy has been used to analyze the hydriding kinetics and to determine microscopic rate parameters associated with surface dissociation of molecular hydrogen, diffusion-controlled transport of atomic hydrogen to bulk regions and hydride formation. Results have been compared to those measured on LaNi₅ and the interest of using such substituted compounds for application in auxiliary power units is discussed.     

Improved hydrogen storage behaviours of nanocrystalline and amorphous Mg2Ni-type alloy by Mn substitution for Ni

The nanocrystalline and amorphous Mg₂Ni-type alloys with nominal compositions of Mg₂Ni_1−xMn_x (x = 0, 0.1, 0.2, 0.3, 0.4) were synthesized by melt spinning technique. The structures of the as-cast and spun alloys were characterized by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage performances were tested by an automatic galvanostatic system. The results show that the as-spun (x = 0) alloy holds 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 hydrogen absorption capacity of the alloys first increases then decreases with rising Mn content, but the hydrogen desorption capacity of the alloys grows with increasing Mn content. Furthermore, the substitution of Mn for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, involving both the discharge capacity and the electrochemical cycle stability. With an increase in the amount of Mn from 0 to 0.4, the discharge capacity of as-spun (30 m/s) alloy grows from 116.7 to 311.5 mAh/g, and its capacity retaining rate at 20th charging and discharging cycle rises from 36.7 to 78.7%.     

Crystal structure and hydrogen storage property of Nd2Ni7 superlattice alloy

This study investigates the crystal structure and Pressure–composition (P–C) isotherm of Nd₂Ni₇ prepared by annealing an arc-melted ingot at 1448 K for 10 h followed by ice-water quenching. The crystal structure was further refined by X-ray Rietveld analysis based on the Ce₂Ni₇-type structure. The lattice parameters were determined as a = 0.5001(1) nm and c = 2.4437(4) nm. A single plateau was observed during the first absorption–desorption cycle. In the first absorption cycle, the maximum hydrogen capacity reached 1.22 H/M (1.58 mass%) at 233 K. The absorption and desorption plateau pressures were approximately 1.0 and 0.002 MPa, respectively. In the first desorption process, 0.63 H/M of hydrogen remained in the sample. Further, a single sloping plateau was observed in the second absorption–desorption process. Heavy peak broadening was observed in the X-ray diffraction (XRD) profile after hydrogenation, with no detection of an amorphous phase.     

Hydrogen absorption and its influence on the thermal stability of Zr65Al10Ni10Cu15 amorphous alloy

The hydrogen absorption properties of Zr₆₅Al₁₀Ni₁₀Cu₁₅ amorphous alloy with a wide supercooled liquid region were evaluated using a Sieverts-type apparatus. The amorphous alloy absorbs 0.34, 0.80 and 0.85 wt.% hydrogen within 10, 6 and 5 min at 373, 473 and 523 K, respectively. According to Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory, the hydrogen absorption activation energy of the amorphous alloy was 1.27 kJ mol⁻¹. The pressure–composition (P–C) isotherms of the amorphous Zr₆₅Al₁₀Ni₁₀Cu₁₅ alloy at 573, 623 and 673 K did not show a plateau, and the hydrogen absorption capacities were 0.8, 1.3 and 1.7 wt.%, respectively. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analysis demonstrated that the thermal stability of the amorphous alloy was improved with an enlarged supercooled liquid region after the hydrogen uptake below 473 K, but was decreased after the hydrogenation above 523 K. The alloy still kept the amorphous structure after hydrogenation at 573 K, and transformed into the crystalline phases of ZrH₂, ZrNi and AlCu after the hydrogenation at 673 K.     

Effect of Mg content on structure,hydrogen storage properties and thermal stability of melt-spun Mgx(LaNi3)100−x alloys

Amorphous Mg_x(LaNi₃)_100−x (x = 40, 50, 60, 70) alloys with ribbon shape (5 mm wide, 0.2 mm thick) have been prepared by rapid solidification, using a melt-spinning technique. Their microstructure, hydrogen storage properties and thermal stability were studied by means of XRD, SEM, PCTPro2000 and DSC analysis, respectively. The results indicated that when Mg_x(LaNi₃)_100−x alloys have been hydrogenated at 573 K under 2 MPa hydrogen pressure, LaH₃ phase is formed in the case of x (x = 40, 50, 60, 70), Mg₂NiH₄ phase formed in the case of x (x = 40, 50, 60, 70), Mg₂NiH_0.3 phase formed in the case of x (x = 40, 50), and MgH₂ phase formed in the case of x = 70. Experimental data of hydrogen desorption kinetics, tested at 523 K, 573 K and 623 K, are in good agreement with Avrami–Erofeev equation. The maximum hydrogen absorption capacity is 2.71 wt.% for Mg₇₀(LaNi₃)₃₀ and 2.35 wt.% for Mg₇₀(LaNi₃)₃₀, the increase of hydrogen desorption capacity is in the order of x = 70 > x = 60 > x = 50 > x = 40. Based on DSC analysis, the activation energies for dehydrogenation of these samples are calculated to be 122 ± 2 kJ/mol (x = 40) > 101 ± 3 kJ/mol (x = 50) > 84 ± 5 kJ/mol (x = 60) > 64 ± 3 kJ/mol (x = 70), which are in agreement with the results of hydrogen desorption kinetics.     

Effect of Cr substitution by Ni on the cycling stability of Mg2Ni alloy using EXAFS

This paper describes the hydrogen storage properties of Mg₂Ni_0.9Cr_0.1 alloy and aims to elucidate the effect of doping Cr on the hydrogen sorption/desorption kinetics upon cycling. Mg₂Ni_0.9Cr_0.1 alloy shows stable absorption capacity, and its absorption/desorption rates further improve after cycling. The calculated activation energy for dehydrogenation was 53 kJ/mol at the 3rd cycle, and decreased to 36 kJ/mol at the 20th cycle. XRD combined with SEM exhibits that Cr dopant substitutes for Mg or Ni after ball milling and the lattice structure remains stable over 20 cycles. EXAFS was used to investigate the local coordination of Ni and Cr atoms in the ball-milled and cycled samples. For the ball-milled sample, the strong Cr–Ni bonds weaken the Cr–Mg bonds, thereby destabilizing all Cr-doped phases. After 20 cycles, the stable Ni₁–Mg₁ bonds may be dominant and control the structural stability of Mg₂Ni phases.     

Hydrogenation and dehydrogenation behaviours of nanocrystalline Mg20Ni10−xCux (x = 0−4) alloys prepared by melt spinning

In order to improve the hydriding and dehydriding kinetics of the Mg₂Ni-type alloys, Ni in the alloy was partially substituted by element Cu, and the nanocrystalline Mg₂Ni-type Mg₂₀Ni_10−xCu_x (x = 0, 1, 2, 3, 4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys were measured using an automatically controlled Sieverts apparatus. The results show that the substitution of Cu for Ni does not change the major phase Mg₂Ni. The hydrogen absorption capacity of the alloys first increases and then decreases with rising Cu content, but the hydrogen desorption capacity of the alloys grows with increasing Cu content. The melt spinning significantly improves the hydrogenation and dehydrogenation capacity and kinetics of the alloys.     

Hydrogenation and structural properties of Gd2Ni7 with superlattice structure

The crystal structure and hydrogenation properties of Ce₂Ni₇-type Gd₂Ni₇ were investigated by X-ray diffraction (XRD) and the hydrogen pressure–composition (P–C) isotherm. Ce₂Ni₇-type Gd₂Ni₇ was obtained by annealing at 1523 K for 12 h and quenching in ice water. Two superlattice reflections (002 and 004) of the Ce₂Ni₇-type were clearly observed at 2θ = 7.3° and 14.6° in the XRD profile. The refined lattice parameters were a = 0.49662(9) nm and c = 2.4255(3) nm, respectively. Two plateaus were clearly observed during the absorption–desorption process in the P–C isotherm. The first and second plateaus were at 0.015 and 0.13 MPa, respectively, in the first desorption. The maximum hydrogen capacity reached was 1.13 H/M. The enthalpy and entropy were calculated as −20 kJ/mol H₂ and −80 J/mol H₂ K, respectively, from the van’t Hoff plot. After the P–C isotherm, the GdNi₅ cell expanded by 2.15%, but the Gd₂Ni₄ cell shrank by 2.83%.     

Kinetic properties of La2Mg17–x wt.% Ni (x = 0–200) hydrogen storage alloys prepared by ball milling

The as-cast La₂Mg₁₇ with different amount of Ni powders were mixed through ball milling to produce a new type of La₂Mg₁₇–x wt.% Ni (x = 50, 100, 150, 200) alloy. The microstructures of the alloys were characterized by XRD technique, the results show that the crystal structure transfers to amorphous one with the increasing amount of Ni powders. La₂Mg₁₇–50 wt.% Ni alloy reaches the highest hydrogen absorption capacity of 5.13 wt.% at 300 °C under 2 MPa hydrogen pressure due to its amorphous structure. Furthermore, La₂Mg₁₇–50 wt.% Ni alloy expresses fast hydriding kinetics and absorbs 4.99 wt.% hydrogen gas in 200 s. The hydrogen desorption ability described as discharge capacity during electrochemical reaction is fade next to La₂Mg₁₇–200 wt.% Ni alloy, attributed to the less Mg₂NiH₄ with lower enthalpies and easier to release H₂. The maximum discharge capacity of La₂Mg₁₇–200 wt.% Ni alloy reaches to exciting 980.90 mAh/g, while the La₂Mg₁₇ alloy is only 18.10 mAh/g with inconspicuous improvement of cycle stability. These dramatic difference in electrochemical performance reflect the consequence of sluggish dehydriding process of La₂Mg₁₇–50 and 100 wt.% Ni alloys again. Whereas La₂Mg₁₇–200 wt.% Ni alloy has lower resistance both on alloy surface and in the bulk.     

Superior hydrogen storage properties of Mg95Ni5 + 10 wt.% nanosized Zr0.7Ti0.3Mn2 + 3 wt.% MWCNT prepared by hydriding combustion synthesis followed by mechanical milling (HCS + MM)

Significant improvement of the hydrogen storage property of the magnesium-based materials was achieved by the process of hydriding combustion synthesis (HCS) followed by mechanical milling (MM) and the addition of nanosized Zr_0.7Ti_0.3Mn₂ and MWCNT. Mg₉₅Ni₅ doped by 10 wt.% nanosized Zr_0.7Ti_0.3Mn₂ and 3 wt.% MWCNT prepared by the process of HCS + MM absorbed 6.07 wt.% hydrogen within 100 s at 373 K in the first hydriding cycle and desorbed 95.1% hydrogen within 1800 s at 523 K. The high hydriding rate remained well and the hydrogen capacity reached 5.58 wt.% within 100 s at 423 K in the 10th cycle. The dehydrogenation activation energy of this system was 83.7 kJ/mol, which was much lower than that of as-received MgH₂. A possible hydrogenation–dehydrogenation mechanism was proposed in terms of the structural features derived from the HCS + MM process and the synergistic catalytic effects of nanosized Zr_0.7Ti_0.3Mn₂ and MWCNT.     

Microstructure and hydrogen permeability of Nb40Hf30Ni30 ternary alloy

The microstructure and hydrogen permeability of the Nb₄₀Hf₃₀Ni₃₀ ternary alloys were investigated in particular. The as-cast Nb₄₀Hf₃₀Ni₃₀ alloy consists of the bcc- (Nb,Hf) solid solution, the B_f-HfNi compound and the fine eutectic phase of {(Nb,Hf) + HfNi}. The annealed Nb₄₀Hf₃₀Ni₃₀ alloy consists of the bcc-(Nb, Hf) solid solution and the fine eutectic phase of {(Nb,Hf) + HfNi}. The as-cast Nb₄₀Hf₃₀Ni₃₀ alloy shows a high Φ value of 4.3 × 10⁻⁸ [mol H₂ m⁻¹ s⁻¹ Pa^−0.5] at 673 K, and for the annealed Nb₄₀Hf₃₀Ni₃₀ alloy, the Φ value is 3.8 × 10⁻⁸ [mol H₂ m⁻¹ s⁻¹ Pa^−0.5] at 673 K. Annealing can’t enhance the hydrogen permeability of the Nb₄₀Hf₃₀Ni₃₀ ternary alloy.     

Thermodynamic simulation of hydrogen based thermochemical energy storage system

The increasing energy demand needs the attention for energy conservation as well as requires the utilisation of renewable sources. In this perspective, hydrogen provides an eco-friendly and regenerative solution toward this matter of concern. Thermochemical energy storage system working on gas-solid interaction is a useful technology for energy storage during the availability of renewable energy sources. It provides the same during unavailability of energy sources. This work presents a performance analysis of metal hydride based thermal energy storage system (MH-TES), which can transform the waste heat into useful high-grade heat output. This system opens new doors to look at renewable energy through better waste heat recovery systems. Experimentally measured PCIs of chosen metal hydride pairs, i.e. LaNi_4.6Al_0.4/La_0.9Ce_0.1Ni₅ (A-1/A-3; pair 1) and LaNi_4.7Al_0.3/La_0.9Ce_0.1Ni₅ (A-2/A-3; pair 2) are employed to estimate the thermodynamic performance of MH-TES at operating temperatures of 298 K, 373 K, 403 K and 423 K as atmospheric temperature (T_atm), waste heat input temperature (T_m), storage temperature (T_s) and upgraded/enhanced heat output temperature (T_h) respectively. It is observed that the system with alloy pair A-1/A-3 shows higher energy storage density of 121.83 kJ/kg with a higher COP of 0.48 as compared to A-2/A-3 pair. This is due to the favourable thermodynamic properties, and the pressure differential between coupled MH beds, which results in higher transferrable hydrogen. Besides, the effect of operating temperatures on COP is studied, which can help to select an optimum temperature range for a particular application.     

Effects of Mg substitution on crystal structure and hydrogenation properties of Pr1−xMgxNi3

The effects of substitution of Pr by Mg in PrNi₃ with a PuNi₃-type structure were investigated using pressure–composition (P–C) isotherm measurements and X-ray diffraction. The unit cell of Pr_0.68Mg_0.32Ni_3.04 contracted anisotropically in comparison to that of PrNi₃. The maximum hydrogen capacity of PrNi₃ reached 1.25 H/M in the first absorption. A plateau region was observed between 0.82 H/M and 1.04 H/M in the first absorption cycle. However, 0.85 H/M of hydrogen remained in the sample after the first full desorption. Pr_0.68Mg_0.32Ni_3.04 showed reversible hydrogenation properties. The maximum hydrogen capacity was 1.22 H/M. The plateau region of Pr_0.68Mg_0.32Ni_3.04 was between 0.08 H/M and 0.87 H/M, which was wider than that of PrNi₃. Pr_0.68Mg_0.32Ni_3.04 retained the PuNi₃-type structure after hydrogenation, whereas the crystal structure of PrNi₃ changed from that of PuNi₃-type to an unknown structure. The structural change in PrNi₃ during hydrogenation was evidently different from that in Pr_0.68Mg_0.32Ni_3.04.