Hydrogen generation by oxidation of “mechanical alloys” of magnesium with iron and copper in aqueous salt solutions

Oxidation processes of magnesium and magnesium “mechanical alloys” with iron and copper (1–15 wt%) in presence of aqueous solutions of sodium, cobalt, nickel and copper chlorides have been investigated. The rate of hydrogen generation increases with the increase of the transition metal content in the “alloys” and levels out for the Mg–Cu system. The overall hydrogen yield does not exceed 92% of theoretical one at the initial solution concentrations of 0.032 M and chloride/Mg molar ratios of 0.0075 (0.85 M and 0.20 for NaCl), but becomes close to 100% at double concentration of the transition metal salt solutions. The electrochemical corrosion mechanism of the magnesium oxidation process has been suggested.     

Effect of ball milling in presence of additives (Graphite,AlCl3, MgCl2 and NaCl) on the hydrolysis performances of Mg17Al12

In most of the Mg–Al alloys, Al forms with Mg the intermetallic compound Mg₁₇Al₁₂. In order to understand the hydrogen production from the Mg–Al alloys waste by the hydrolysis reaction in “model” seawater (i.e. 3.5 wt % NaCl), hydrolysis with Mg₁₇Al₁₂ was investigated. The effect of ball milling time, the nature of the additives (graphite, NaCl, MgCl₂ and AlCl₃) and the synergetic effects of both graphite and AlCl₃ were investigated. It has been established that increasing ball milling time up to 5 h is necessary to activate the intermetallic and to decrease sufficiently its crystallites and particles size. On one hand, the presence of AlCl₃ provides the best hydrolysis performance (14% of the theoretical hydrogen volume in 1 h). On the other hand, the mixture obtained by simultaneous addition of graphite and AlCl₃ shows the best hydrolysis performances with 16% of the theoretical H₂ volume reached in 1 h.     

Effects of Zr addition on electrochemical characteristics of MgTiMnNi hydrogen storage alloys

The electrochemical hydrogen storage properties of 25 h milled Mg_0.80Ti_0.175Mn_0.025Zr_xNi_1-x (x = 0, 0.025, 0.05, 0.1) quinary alloys were investigated. The substitution of Zr for Mg or Ni leads to an increase in structural disorder and amorphization. Thus, the maximum discharge capacity and the cycling stability of MgNi-based alloys can be enhanced. The x-ray diffraction patterns indicate that all additive elements are entirely dissolved in the synthesized alloys, and amorphous structure was successfully obtained by 25 h milling. Among the milled alloys, the Mg_0.80Ti_0.175Mn_0.025Zr_0.10Ni_0.90 alloy exhibited the best discharge capacity of 604 mA h g⁻¹ at the initial charge/discharge cycle. The obtained results demonstrate that using multi-component compositions is beneficial for enhancing the structural and cyclic stability of MgNi-based alloys. Therefore, substituting additive elements for Mg or Ni may offer impressive performance for efficient hydrogen storage applications.     

Dehydriding and re-hydriding properties of high-energy ball milled LiBH4 + MgH2 mixtures

Here we report the first investigation of the dehydriding and re-hydriding properties of 2LiBH₄ + MgH₂ mixtures in the solid state. Such a study is made possible by high-energy ball milling of 2LiBH₄ + MgH₂ mixtures at liquid nitrogen temperature with the addition of graphite. The 2LiBH₄ + MgH₂ mixture ball milled under this condition exhibits a 5-fold increase in the released hydrogen at 265 °C when compared with ineffectively ball milled counterparts. Furthermore, both LiBH₄ and MgH₂ contribute to hydrogen release in the solid state. The isothermal dehydriding/re-hydriding cycles at 265 °C reveal that re-hydriding is dominated by re-hydriding of Mg. These unusual phenomena are explained based on the formation of nanocrystalline and amorphous phases, the increased defect concentration in crystalline compounds, and possible catalytic effects of Mg, MgH₂ and LiBH₄ on their dehydriding and re-hydriding properties.     

Remarkably improved hydrogen storage properties of carbon layers covered nanocrystalline Mg with certain air stability

Different nanocrystalline magnesium with carbon layers were successfully synthesized via a facile wet-chemical ball milling method for 20, 30 and 40 h, respectively. Based on Scherrer formula and X-ray diffraction results, the average crystallite size of all the three samples was below 30 nm. TEM observations showed that the hydrogenated Mg particles were covered with carbon layers. Moreover, the 40 h ball milled Mg sample showed outstanding hydrogen storage performance especially in the aspect of hydrogen absorption. The as-prepared sample started to take up hydrogen at nearly room temperature and eventually absorbed 6.8 wt% hydrogen at 200 °C. The apparent activation energy (E_a) of hydrogen absorption for the sample was decreased to 26.7 kJ/mol, much lower than that of other reported systems. For the dehydrogenation experiments, the hydrogenated sample could start to release hydrogen at about 275 °C and 6.5 wt% hydrogen was desorbed in 20 min at 325 °C. Interestingly, the prepared samples showed noteworthy air stability. Been placed in the air for 60 min, the dehydrogenation kinetics and hydrogen capacity of the three samples were basically unchanged, making it possible to be used in future commercial applications.     

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.     

Production of an Mg/Mg2Ni lamellar composite for generating H2 and the recycling of the post-H2 generation residue to nickel powder

The magnesium hydrolyzing reaction was catalyzed in situ using a layered Mg₂Ni compound, rapidly producing hydrogen in NaCl solution. The post-H₂ generation residue (mixture of Mg(OH)₂ and Mg₂Ni catalyst) was recycled to recover pure Ni powder from the waste mixture. Pure Mg (153 g) and pure Ni (47 g) in a eutectic composition were easily melted to form a molten alloy by a super-high-frequency (35,000 Hz) induction furnace. The lamellar material had an Mg/Mg₂Ni/Mg/Mg₂Ni… layered structure, in which each layer was ∼0.8 μm thick; Mg was an anodic phase and Mg₂Ni was a cathodic phase (the catalyst). Bulk Mg/Mg₂Ni composite alloy contains many microgalvanic cells. Owing to the lamellar microstructure, no dense hydrated oxide film that might have caused surface passivation was found, allowing continuous H₂ generation until no magnesium remained to participate in the hydrolysis. The activation energy of the hydrolysis reaction in simulated sea water was ∼36.35 kJ mol⁻¹.     

Effect of ball milling strategy (milling device for scaling-up) on the hydrolysis performance of Mg alloy waste

Ball milling strategy is of prime importance on the hydrolysis performance of Mg alloy waste. The effect of milling device (e.g. Fritsch Pulverisette 6 (P6) and Australian Uni-Ball-II (UB)), milling atmosphere (H₂ and Ar), milling time, nature of the additives graphite and AlCl₃ and synergetic effect by chronological or simultaneous addition were examined. An equivalence between both mills was established and it was shown that the process with the UB is 10 times longer than that with the P6 to acquire a similar material. Mg alloy milled without additives in the P6 under Ar for 10 h improves the hydrolysis performance. Using a single additive, the best hydrolysis performances are obtained with graphite (yield of 95% of total capacity reached in 5 minutes) due to the formation of a protective graphite layer. By incorporating both additives sequentially, the best material, from the hydrogen production point of view, was Mg alloy milled with G for 2 h and then with AlCl₃ for 2 extra hours (full hydrolysis in 5 minutes). Mg alloy milled with the P6 were compared to those milled with the UB. Mg alloy milled with graphite or with sequential addition of G and AlCl₃ under Ar generated more than 90% of their total capacity. Our results confirm that laboratory-milling strategy can be scaled-up to industrial scale.     

Study on the influence of Mg content on the risk of hydrogen production from waste alloy dust in wet dust collector

We use a proprietary automatic Al–Mg alloy–water reaction test apparatus to compare the hydrogen evolution profiles of Al-xMg (x = 10%,20%) with different particle sizes, characterize the waste Al-xMg alloy dust particles before and after reaction through SEM, EDS, and XRD, and present a three-stage four-step hydrogen evolution model of Al-xMg (x ≤ 35%) alloy dust particles. It is discovered that the reaction of the Al–Mg alloy in water is a hydrogen evolution–adsorption–slow diffusion process. The particular β-Al₃Mg₂ in Al-xMg (x ≤ 35%) will adsorb the resulting hydrogen to form MgH⁺ and adhere to the surface of the particles. As the Mg content in the alloy increases, the hydrogen evolution reduces. The entire process lasts around 5–6 h, with maximum hydrogen conversion rate of 54% (Al–10%Mg, d (50) = 12 μm, α = 0.544). Our hydrogen evolution model provides very useful theoretical references for avoiding hydrogen explosion in Al–Mg alloy manufacturing facilities.     

Effect of graphite (GR) content on electrochemical hydrogen storage performances of nanocrystalline and amorphous La9Ce1Mg80Ni5–Ni–GR composites synthesized by mechanical milling

The Mg–Ni-based alloy La₉Ce₁Mg₈₀Ni₅ was fabricated by a vacuum induction furnace with high purity helium gas. The surface modification of the as-cast alloys was operated by mechanical coating Ni and graphite (GR). The composites La₉Ce₁Mg₈₀Ni₅-200 wt% Ni-x wt.% GR (x = 0–4) with nanocrystalline and amorphous structures were synthesized by mechanical milling. Adding appropriate GR brings on the enhancement of ball-milling efficiency and inhibits the agglomeration of alloy powders. Furthermore, the discharge capacity of the composites obtains the maximal values with an optimized GR percentage. Increasing GR content from 0 to 4, the capacity retention rate at 20th cycle (S₂₀ = C₂₀/C_max) of the 20 h milled composite improves from 72.2% to 74.3% and that of the 80 h milled specimen changes from 54.4% to 56.9%. Electrochemical tests indicate that with the optimization of GR percentage, the composites can get the best electrochemical kinetic property, such as the highest HRD value, the highest hydrogen diffusion coefficient and the lowest charge transfer resistance.     

Fabrication of Mg–Ni–Sn alloys for fast hydrogen generation in seawater

Mg-2.7Ni-x wt.% Sn(x = 0–2) alloys were fabricated to promote hydrogen generation kinetics of Mg-2.7Ni alloy. The Sn in Mg-2.7Ni-Sn alloys exists as Mg₂Sn phase at the grain boundary and solid solution at the Mg matrix. The Mg₂Sn at the grain boundary acts as the initiation site for pitting corrosion and the dissolved Sn in the alloy causes pitting corrosion by locally breaking the surface oxide film in the Mg matrix in seawater. The Mg-2.7Ni-1Sn alloy showed an excellent hydrogen generation rate of 28.71 ml min^?1 g^?1, which is 1700 times faster than that of pure Mg due to the combined action of galvanic and intergranular corrosion as well as pitting corrosion in seawater. As the solution temperature was increased from 30 to 70 °C, the hydrogen generation rate from the hydrolysis of the Mg-2.7Ni-1Sn alloy was dramatically increased from 34 to 257.3 ml min^?1 g^?1. The activation energy for the hydrolysis of Mg was calculated to be 43.13 kJ mol^?1.     

Disposable hydrogen generators: Magnesium hydride oxidation in aqueous salts solutions

The impact of mechanochemical activation and methods of addition of non-hydrolyzing salts of NaCl, NH₄Cl, NH₄Br и MgCl₂?(either dry powder or solution) on the reaction rate and yield of hydrogen production upon magnesium hydride oxidation by water was investigated. It was established that addition of halides increases the hydrogen yield from 22% to 99% (of theoretical value) while the rate of hydrogen production has increased from ～220 to 1700 mL/min g (MgH₂). The addition of dry salts during the mechanochemical treatment of the hydride always results in much higher reaction rate compared to the use of the same salt solutions. It was observed that activation by NH₄Cl and MgCl₂ results in bell-shaped change in the hydrogen release rate. Of all evaluated halide salt activators, the greatest overall yield (～99%) was achieved in the presence of 0.17 M NaCl solution. The reaction rate at these conditions was rather slow; it took up to 4 h to complete the oxidation. The highest rate of oxidation, when 94% of theoretical yield was achieved in 3 min, was observed in the presence of 0.85 M NH₄Br.     

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.     

Mechanical milling of Mg,Ni and Y powder mixture and investigating the effects of produced nanostructured MgNi4Y on hydrogen desorption properties of MgH2

It has been reported that intermetallic compounds could be used to improve hydrogen storage properties of Mg-based alloys. In this study, an attempt was made to synthesize the MgNi₄Y compound from pure Ni, Mg and Y elemental powders via the combination of mechanical milling and heat treatment methods. In this regard, powders were ball milled in different conditions and then heat treated at 400 and 600 °C for 4 h to investigate the effect of temperature on the formation of MgNi₄Y intermetallic compound. The characteristics of mixtures were evaluated via (XRD) and (SEM) methods. It was found from the results of XRD analysis that ternary intermetallic compound was not formed completely via ball milling alone. Nanostructured intermetallic compound was formed after heat treatment of milled powder at 600 °C for 25 h. Furthermore, addition of 5 and 10 wt% of the produced intermetallic compound to MgH₂ decreased hydrogen desorption temperature and increased released hydrogen content.     

Magnesium and iron loaded hollow glass microspheres (HGMs) for hydrogen storage

The development of a safe and efficient method for hydrogen storage is essential for the use of hydrogen with fuel cells for vehicular applications. Hollow glass microspheres (HGMs) have characteristics suitable for hydrogen storage and are expected to be a potential hydrogen carrier to be used for energy release applications. The HGMs with 10–100 μm diameters, 100–1000 Å pore width and 3–8 μm wall thicknesses are expected to be useful for hydrogen storage. In our research we have prepared HGMs from amber glass powder of particle size 63–75 μm using flame spheroidisation method. The HGMs samples with magnesium and iron loading were also prepared to improve the heat transfer property and thereby increase the hydrogen storage capacity of the product. The feed glass powder was impregnated with calculated amount of magnesium nitrate hexahydrate salt solution to get 0.2–3.0 wt% Mg loading on HGMs. Required amount of ferrous chloride tetrahydrate solution was mixed thoroughly with the glass feed powder to prepare 0.2–2 wt% Fe loaded HGMs. Characterizations of all the HGMs samples were done using FEG-SEM, ESEM and FTIR techniques. Adsorption of hydrogen on all the Fe and Mg loaded HGMs at 10 bar pressure was conducted at room temperature and at 200 °C, for 5 h. The hydrogen adsorption capacity of Fe loaded sample was about 0.56 and 0.21 weight percent for Fe loading 0.5 and 2.0 weight percentage respectively. The magnesium loaded samples showed an increase of hydrogen adsorption from 1.23 to 2.0 weight percentage when the magnesium loading percentage was increased from 0 to 2.0. When the magnesium loading on HGMs was increased beyond 2%, formation of nano-crystals of MgO and Mg was seen on the HGMs leading to pore closure and thereby reduction in hydrogen storage capacity.     

Effect of V,Nb, Ti and graphite additions on the hydrogen desorption temperature of magnesium hydride

In this study the effects of mechanical milling with 5 wt.% of additives (V, Nb, Ti and Graphite) on the hydrogen desorption temperature of the magnesium hydride (MgH₂) were studied. The powder mixtures were mechanically milled for 2 h. X-ray diffraction (XRD), scanning electron microscope (SEM), and optical microscope (OM) techniques were used for the structural and morphological characterization of powders. Differential scanning calorimeter (DSC) was used to investigate the effects of the mechanical milling with additives on the hydrogen desorption temperature of the magnesium hydride powder. DSC results show that the hydrogen desorption temperatures of mechanically milled MgH₂ with additives are depressed about ∼40–50 °C compared with that of as-received MgH₂. The particle size analysis results indicate that decrease of the particle size of powders leads to a decrease of the hydrogen desorption temperature. Moreover, increasing specific surface area can also contribute to a decrease on the hydrogen desorption temperature.     

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.     

Hydrogen generation by the hydrolysis of magnesium–aluminum–iron material in aqueous solutions

Highly activated Mg–Al–Fe materials are prepared from powder by mechanical ball milling method for hydrogen generation. The hydrolysis characteristics of Mg–Al–Fe materials in aqueous solutions under different experimental conditions are carefully investigated. The results show that the hydrolysis reactivity of Mg–Al–Fe material can be significantly improved by increasing the ball milling time and Fe content. The increase of NaCl solution concentration and initial temperature is also found to promote the hydrogen generation reaction. At 25 °C, the Mg60–Al30–Fe10 (wt%) material ball-milled for 4 h shows the best performance in 0.6 mol L⁻¹ NaCl solution, and the reaction can produce 1013.33 ml g⁻¹ hydrogen with a maximum hydrogen generation rate of 499.50 ml min⁻¹ g⁻¹. In comparison to NaCl solution, natural seawater is found to have an inhibiting effect on the hydrolysis of Mg–Al–Fe material. Especially, the presence of Mg²⁺ and Ca²⁺ in seawater can greatly reduce the hydrogen conversion yield, and the SO₄²⁻ can decrease the hydrogen generation rate.     

Hydrogen production for micro-fuel-cell from activated Al–Sn–Zn–X (X: hydride or halide) mixture in water

A systematic investigation of hydrogen production from milled Al–Sn–Zn–X (X: hydride or halide) mixtures in pure water was performed at room temperature. The hydrolysis mechanism of the mixtures was based on the work of micro-galvanic cell between aluminum and tin in water where aluminum reacted with water to generate AlOOH (Boehmite) and hydrogen. It was found that many effects such as milling time, temperature, additives and mass ratio had a significant role in the hydrogen production rate, especially that of the additives (hydride or halide) led to reduction of crystallite size and accumulation of uniform mixing. They also produced a lot of heat and the conductive ions which simulated the work of micro-galvanic cell. The milled Al–Sn–Zn–X (X: hydride or halide) mixtures had high reactivity and Al–Sn–Zn–MgH₂ mixture produced 790 mL g^?1 hydrogen in 5 min of the hydrolysis reaction with the activation energy of 17.570 kJ mol^?1, corresponding to 7.04 wt.% hydrogen excluding water mass. Therefore, a new method of CO₂ free and safe hydrogen production for micro-fuel-cell was obtained from the activated aluminum alloys in water.     

Effects of hydrogen addition on the explosion characteristics of n-hexane/air mixtures

To study the effects of hydrogen addition on the explosion characteristics (the explosion pressure and maximum rate of pressure rise) of n-hexane/air mixtures, experiments were performed in a cylindrical vessel at 100 kPa, 353 K, with equivalence ratios of 0.8–1.7 and hydrogen addition range from 0% to 80%. Concurrently, flame images were captured by high-speed schlieren photography to study the burning performance. The results indicate that both the explosion pressure and maximum pressure rise rate increase with the increase in hydrogen addition in terms of the lean n-hexane/hydrogen/air mixtures. With respect to the richer mixtures, however, the inverse tendency is observed. With increasing hydrogen fractions, the explosion pressure and maximum pressure rise rate decrease. The peak values of the explosion pressure and maximum pressure rise rate shift to the leaner mixture with increased hydrogen proportion. Moreover, the laminar burning velocities of n-hexane/hydrogen/air mixture were also obtained via the expanding spherical method and the pressure-time histories, respectively. Variation of laminar burning velocity with hydrogen proportion from both methods were studied as well, and the results show that the laminar burning velocity changes significantly under different hydrogen addition.