Effects of rapid quenching on structure and cycle stability of La-Mg-Ni-Co type hydrogen storage alloy

In order to improve the cycle stability of La-Mg-Ni-Co type alloy electrode, rapid quenching technology was employed. The effects of rapid quenching on the microstructure and cycle stability of the alloy were investigated. The obtained results show that the La2Mg(Ni0.85Co0.15)9M0.1 (M=B, Cr) alloy electrodes are composed of (La, Mg)Ni3 phase, LaNi5 phase and a small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast MB alloy, and the Ni2B phase in the alloy nearly disappears after rapid quenching. Rapid quenching technology can slightly improve the cycling life of the alloy. When the quenching rate increases from 0 m·s-1 (As-cast is defined as quenching rate of 0 m·s-1) to 30 m·s-1, the cycle lives of the MB, MCr alloys enhance from 86 and 87 cycles to 106 and 119 cycles, respectively. On the other hand, the average capacity decay rates of the MB, MCr alloys decrease from 1.7172 and 1.7178 mAh·g-1·cycle-1 to 1.5751 and 1.3060 mAh·g-1·cycle-1 after 86 charge-discharges cycling, respectively.

Structure and electrochemical properties of La-Mg-Ni system hydrogen storage alloys with different Co contents

The structure and electrochemical properties of the La0.7Mg0.3Ni3.4-xMn0.1Cox （x=01.05） hydrogen storage alloys were investigated. The crystal structure and the lattice parameters of the alloys were analyzed by X-ray diffractometry and Rietveld method. Electrochemical properties of the alloys including p—c—t curves, discharge capacity, discharge capacity retention were studied. The results show that （La, Mg）Ni3 and LaNi5 are the main phases of all the alloys. The plateau pressure for hydrogen absorption/desorption decreases and the hydrogen storage capacity firstly increases and subsequently decreases with increasing Co content. The values of the maximum discharge capacity of the alloy electrodes remain in range of 395.3403.1mA·h/g in spite of the change of Co content. The cycling stability of the alloy electrodes is greatly improved with increasing Co content, which is attributed to the suppression of the cell volume expansion during hydriding, leading the pulverization of the alloy particles lowered and the oxidation/corrosion of the active elements reduced.

Improved Hydrogen Storage Kinetics of Nanocrystalline and Amorphous Mg-Nd-Ni-Cubased Mg_2Ni-type Alloys by Adding Nd

In order to improve the gaseous and electrochemical hydrogen storage kinetics of the M2Nitype alloy, the elements Cu and Nd were added in the alloy. The nanocrystalline and amorphous Mg2Ni-type alloys with the composition of（Mg24Ni10Cu2）100-xNdx（x = 0, 5, 10, 15, 20） were prepared by melt spinning technology. The effects of Nd content on the structures and hydrogen storage kinetics of the alloys were investigated. The characterization by X-ray diffraction（XRD）, transmission electron microscopy（TEM） and scanning electron microscopy（SEM） reveals that all the as-cast alloys hold multiphase structures, containing Mg2Ni-type major phase as well as some secondary phases Mg6Ni, Nd5Mg41, and Nd Ni, whose amounts clearly grow with increasing Nd content. Furthermore, the as-spun Nd-free alloy displays an entire nanocrystalline structure, whereas the as-spun Nd-added alloys hold a mixed structure of nanocrystalline and amorphous structure and the amorphization degree of the alloys visibly increases with the rising of the Nd content, suggesting that the addition of Nd facilitates the glass forming in the Mg2Ni-type alloy. The measurement of the hydrogen storage kinetics indicates that the addition of Nd significantly improves the gaseous and electrochemical hydrogen storage kinetics of the alloys. The addition of Nd enhances the diffusion ability of hydrogen atoms in the alloy, but it impairs the charge-transfer reaction on the surface of the alloy electrode, which makes the high rate discharge ability（HRD） of the alloy electrode fi rst mount up and then go down with the growing of Nd content.

Structures and properties of La-Mg-Ni system hydrogen storage alloys

The double-roller rapid quenching technology was successfully used to prepare La-Mg-Ni system hydrogen storage alloys. The effects of magnesium content and heat-treatment process on the alloys properties were studied. When the alloy with 1.09%(mass fraction) Mg is heat treated at 900 ℃ for 4 h,its discharge capacity is more than 380 mA·h/g at 0.2C,and the cyclic life is beyond 500 counts at 2C. By XRD and PCI analyzing,the results show that the alloys are composed of LaNi5 and LaNi3 phase. The hydrogen absorption/desorption pressure of the alloy increases,so does the slope of plateau,and the plateau becomes broad first and narrow again as Mg content increases. This method is simple to be suitable for production on a large scale.

Gaseous and Electrochemical Hydrogen Storage Kinetics of As-quenched Nanocrystalline and Amorphous Mg_2Ni-type Alloys

The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox （x = 0, 0.1, 0.2, 0.3, 0.4） alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo2 and Mg instead of altering the major phase Mg2Ni. No amorphous phase is detected in the as-quenched Co- ffee alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient （D） along with the limiting current density （IL） and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.

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.

Effect of praseodymium substitution for lanthanum on structure and properties of La_(0.65-x)Pr_xNd_(0.12)Mg_(0.23)Ni_(3.4)Al_(0.1)(x=0.00–0.20) hydrogen storage alloys

In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system （AB3.5-type） hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1（x=0, 0.10, 0.15, 0.2） hydrogen storage alloys were prepared. X-ray diffraction （XRD）, scanning electron microscopy （SEM） and energy dispersive spectrometer （EDS） analyses revealed that two alloys （x=0.0 and 0.10） were composed of （La,Mg）2（Ni,Al）7 phase, La（Ni,A1）5 phase and （La,Mg）Ni2 phase, while other alloys （x=0.15 and 0.20） consisted of （La,Mg）2（Ni,A1）7 phase, La（Ni,A1）5 phase, （La,Mg）Ni2 phase and （La,Mg）（Ni,A1）3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Electrochemical studies showed that the discharge capacity decreased from 360 mAh/g （x=-0.00） to 335 mAh/g （x=-0.20） as x increased. But the high-rate dischargeability （HRD） of alloy electrodes increased from 26% （x=0.00） to 56% （x=-0.20） at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.

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).

Hydrogen storage properties of Mg-doped Ti_(1.2)Fe alloys synthesized by mechanical alloying

Hydrogen storage properties and phase components of Mg doped TiFe alloys, that were prepared by Ti, Fe and Mg metal powders using a mechanical alloying technique, were studied. XRD analyses show that the main phase of all the Mg doped Ti 1.2 Fe alloys is the TiFe phase. Some TiFe 2 phase and α Ti phase exist as secondary phases and Mg is dispersed in the alloy matrix. 3% Mg doped and 5% Mg doped Ti 1.2 Fe alloy samples can be fully activated within three hydriding/dehydriding cycles at room temperature and the hydrogen storage capacities of the alloys can reach 222 mL/g and 198 mL/g, respectively. Both two samples exhibit only one plateau region in their P C T curves with a low hydrogen absorption/desorption pressure hysteresis. The effect and mechanism of Mg addition as well as overstoichiometric Ti on the activation properties and hydrogen storage capacities of the alloys was also discussed.

Influences of stoichiometric ratio B/A on structures and electrochemical behaviors of La_(0.75)Mg_(0.25)Ni_(3.5)M_x (M=Ni,Co;x=0-0.6) hydrogen storage alloys

In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of the AB3.5-4.1-type electrode alloys, the La-Mg-Ni-Co system La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x= 0, 0.2, 0.4, 0.6) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The results show that the structures and electrochemical performances of the alloys are closely relevant to the B/A ratio. All the alloys exhibit a multiphase structure, including two major phases, (La, Mg)2Ni7 and LaNi5, and a residual phase LaNi2, and with rising ratio B/A, the (La,Mg)2Ni7 phase decreases and the LaNi5 phase increases significantly. When ratio B/A=3.7, the alloys obtain the maximum discharge capacities. The high rate discharge(HRD) capability of the alloy (M=Ni) monotonously rises with growing B/A ratio, but that of the alloy (M=Co) first mounts up then declines. The cycle stability of the alloy (M=Co) monotonously increases with rising B/A ratio, but it first decreases slightly then increases for the alloy (M=Ni). The discharge potential of the alloy (M=Ni) declines with increasing B/A ratio (x>0.2), but for the alloy (M=Co), the result is contrary. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed ratio B/A=3.7, the Co substitution enhances the discharge capacity from 365.7 to 401.8 mA·h/g, the capacity retention ratio (S100) after 100 charging-discharging cycles from 50.32% to 53.26% and the HRD from 88.65% to 90.69%.

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.

Influence of addition of Cu(OH)_2 to KOH alkaline electrolyte on electrochemical properties of La_2Mg_(0.9)Al_(0.1)Ni_(7.5)Co_(1.5) hydrogen storage alloy electrode

The influence of the addition of Cu(OH)2 to 6 mol/L KOH alkaline electrolyte on the electrochemical properties of La2Mg0.9Al0.1Ni7.5Co1.5 hydrogen storage alloy electrode was investigated by electron probe X-ray microanalysis(EPMA),X-ray diffraction(XRD) and electrochemical measurements. EPMA micrographs and XRD patterns show that the surface of the hydride electrode is plated by metal copper film. The thickness and compactness of Cu film increase with the increment of charge-discharge cycle number. The copper film of the hydride electrode surface can keep the hydrogen storage alloy particle in the electrode interior from oxidizing availably. The addition of Cu(OH)2 to alkaline electrolyte lowers the activation property and the high rate dischargeability of the La2Mg0.9Al0.1Ni7.5Co1.5 hydride electrode,but has no negative effect on the maximum discharge capacity of the hydride electrode. Moreover,it is effective to improve the cyclic stability of the hydride electrode utilizing electrodeposit Cu film on the La2Mg0.9Al0.1Ni7.5Co1.5 hydride electrodes surface.

Effects of doping Fe and Al on microstructure and electrochemical characteristics of Mg-based hydrogen storage alloys

The Mg-based hydrogen storage alloys Mg2Ni, Mg2Ni0.7Fe0.3 and Mg1.7Al0.3Ni were successfully synthesized by a two-step process (sintering and ball milling). The crystal structure and microstructure were examined by X-ray diffraction, Scanning Electron Microscope and Malvern particle size analyzer. New phase appears in the tripe alloys doped with Al and Fe, and the particle size ranges from 3 μm to 5 μm. The electrochemical performance studies indicate that the partial substitution of Al for Mg, and Fe for Ni significantly improve the cycle life, reversibility of hydrogen absorption and desorption. The diffusion process is the control step in the electrode reaction of hydrogen storage alloys.

Geometric Effects of La_(1+x)Mg_(2-x)Ni_9 (x=0.0~1.0) Ternary Alloys on Their Hydrogen Storage Capacities

Structural analysis was made using X-ray diffraction (XRD) Rietveld refinement on a series of La1+xMg2-xNi9 (x=0.0-1.0) ternary alloys. Results showed that each of La1+xMg2-xNi9 alloys was a PuNi3-type structure stacked by LaNi5 and (La, Mg) Ni2 blocks. Electrochemical tests revealed that discharge abilities of these La-Mg-Ni ternary alloys mainly depended on their atomic distances between (La, Mg) and Ni, which could be modified by varying the atomic ratios of La/Mg.

Preparation of low cobalt high rate discharge hydrogen storage alloy MlNi_(3.85)Co_(0.45) Mn_(0.4)Al_(0.3)X_(0.1)(X=Mg,Si,Sn)

The non stoichiometric high rate discharge hydrogen storage alloys series MlNi 3.85 Co 0.45 Mn 0.4 Al 0.3 X 0.1 (Ml represents the lanthanum rich mischmetal, and X=Mg,Si,Sn) were prepared. The XRD and EDS results show that the high catalysis active miscellaneous La 2Ni 7 phase forms except for main phase LaNi 5 in the alloy body. The high rate discharge performance of hydrogen storage alloys electrode was improved because of the formation of La 2Ni 7 phase. The discharge capacities at 0.2C, 1C and 5C discharge rate reach 320 mAh·g -1 , 300 mAh·g -1 and 260 mAh·g -1 respectively when X is (Mg+Si). At the same scanning rate of circular volt—ampere testing, the surface anode oxidation peak current and peak area of the alloy containing (Mg+Si) electrode are far more larger than that of the high cobalt alloy MlNi 3.55 Co 0.75 Mn 0.4 Al 0.3 (AB 5). Furthermore, the cobalt content of the hydrogen storage alloy containing (Mg+Si) decreases by 40% and the high rate discharge performance improves obviously compare to high cobalt AB 5 alloys, it is promising that the hydrogen storage alloy containing (Mg+Si) becomes to an ideal dynamic battery cathode material.

Gaseous and Electrochemical Hydrogen Storage Properties of Nanocrystalline Mg₂Ni-Type Alloys Prepared by Melt Spinning

A partial substitution of Ni by Cu has been carried out in order to improve the hydrogen storage characteristics of the Mg2Ni-type alloys. The nanocrystalline Mg20Ni10-xCux (x = 0, 1, 2, 3, 4) alloys are synthesized by the melt-spinning technique. The structures of the as-cast and spun alloys have been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM). The electrochemical performances were evaluated by an automatic galvanostatic system. The hydrogen absorption and desorption kinetics of the alloys were determined by using an automatically controlled Sieverts apparatus. The results indicate that the substitution of Cu for Ni does not alter the major phase Mg2Ni. The Cu substitution significantly ameliorates the electrochemical hydrogen storage performances of alloys, involving both the discharge capacity and the cycle stability. The hydrogen absorption capacity of alloys has been observed to be first increase and then decrease with an increase in the Cu contents. However, the hydrogen desorption capacity of the alloys exhibit a monotonous growth with an increase in the Cu contents.

球磨态La-Y-Mg-Ni合金的显微组织和储氢性能

为了提高La-Y-Mg-Ni合金的储氢性能,通过对铸态合金进行5~30 h的球磨,制备具有非晶和纳米晶结构的La_(1.7)Y_(0.3)Mg_(16)Ni合金,并研究显微组织对储氢性能的影响及其机理。结果表明,随着球磨时间的延长,合金的结晶度、晶粒尺寸和粒径减小,非晶相增加。纳米晶相和非晶相的双重调节作用导致储氢动力学性能先加快,后减慢。经过15 h球磨的合金具有最好的吸、放氢动力学特性,在373 K下10 min内可以吸收3.10%(质量分数)的氢气,其放氢活化能最低,为71.2 k J/mol。球磨不同时间的合金的热力学性能的变化很小,球磨15 h后合金的放氢焓变最低,为72.9 k J/mol。

An overview of progress in Mg-based hydrogen storage films

Mg-based hydrogen storage materials are considered to be one of the most promising solid-state hydrogen storage materials due to their large hydrogen storage capacity and low cost. However, slow hydrogen absorption/desorption rate and excessive hydrogen absorption/desorption temperature limit the application of Mg-based hydrogen storage materials.The present paper reviews the advances in the research of Mg-based hydrogen storage film in recent years, including the advantage of the film, the function theory of fabricating method and its functional theory, and the influencing factors in the technological process. The research status worldwide is introduced in detail. By comparing pure Mg, Pd-caped Mg, nonpalladium capped Mg, and Mg alloy hydrogen storage films, an ideal tendency for producing Mg-based film is pointed out,for example, looking for a cheap metal element to replace the high-priced Pd, compositing Mg film with other hydrogen storage alloy of catalytic elements, and so on.

MgH_2-Ti/Cr(AMORPHOUS)COMPOSITE FOR HYDROGEN STORAGE

Ti/Cr (atomic ratio 3:4) amorphous alloy was prepared by ball milling the rapidly quenched Ti/Cr ribbons for 30h, and then milled with MgH_2 for 50 h under Ar atmosphere to obtain MgH_2-30wt. % Ti/Cr composite. The XRD results indicate that MgH_2 decomposed partly during ball milling process. The brittle MgH_2 and the mechanical driving force resulted in a highly dispersive distribution of the Ti/Cr amorphous phase in the Mg matrix. The favorable hydrogenation performance is mainly attributed to the com...

CHARACTERISTICS OF METAL-HYDROGEN INTERACTION IN HYDROGEN STORAGE ALLOYS

The electronic structures are calculated by the DV-Xa molecular orbital method employing small model clusters in order to clarify the roles of the hydride forming elements, A, (e.g., La, Zr Ti, Mg) and non-forming elements, B, (e.g., Ni, Mn, Fe) in hydrogen storage alloys. It is confirmed from this calculation that hydrogen interacts more strongly with hydride non-forming elements, B, than hydride forming elements, A, in agreement with our previous calculations. However,the B-H interaction is enhanced only when some A element exists in the neighborhood. Otherwise, such a B-H interaction never operates in the alloy. In this sense,the coexistence of A and B elements are essential in the constitution of hydrogen storage alloys. Also, it is shown that the A/B compositional ratio of hydrogen storage alloys is understood in terms of a simple parameter, 2Bo(A - B) / /Bo(A - A)+ Bo(B-B)], where the Bo(A-B), Bo(A-A) and the Bo(B-B) are the bond strengths between atoms given in the parentheses.