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.

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.

Synergy of inside doped metals–Outside coated graphene to enhance hydrogen storage in magnesium-based alloys

Grain growth of magnesium(Mg)and its hydride is one of the main reasons for kinetic and capacity degradation during the hydrogen absorption and desorption cycles.To solve this problem,herein we propose a novel method involving synergistic effect of inside embedded metals and outside coated graphene to limit the growth of Mg and its hydride grains.The graphene coated Mg-Y-Al alloys were selected as a model system for demonstrating this positive effect where the Mg_(91)Y_(3)Al_(6)alloy was first prepared by rapidly solidified method and then high-pressure milled with 5 wt%graphene upon 5 MPa hydrogen gas for obtaining in-situ formed YAl_(2)and YH_(3)embedded in the MgH_(2)matrix with graphene shell(denoted as MgH_(2)-Y-Al@GR).In comparison to pure MgH_(2),the obtained MgH_(2)-Y-Al@GR composites deliver much better kinetics and more stable cyclic performance.For instance,the MgH_(2)-Y-Al@GR can release about 6.1 wt%H_(2)within 30 min at 300℃ but pure MgH_(2)only desorbs∼1.5 wt%H_(2).The activation energy for desorption of MgH_(2)-Y-Al@GR samples is calculated to be 75.3±9.1 kJ/mol that is much lower than approximately 160 kJ/mol for pure MgH_(2).Moreover,its capacity retention is promoted from∼57%of pure MgH_(2)to∼84%after 50th cycles without obvious particle agglomeration and grain growth.The synergistic effect of outside graphene coating with inside embedded metals which could provide a huge number of active sites for catalysis as well as inhibit the grain growth of Mg and its hydride is believed to be responsible for these.

Key technology and application of AB_(2) hydrogen storage alloy in fuel cell hydrogen supply system

At present,there is limited research on the application of fuel cell power generation system technology using solid hydrogen storage materials,especially in hydrogen-assisted two-wheelers.Considering the disadvantages of low hydrogen storage capacity and poor kinetics of hydrogen storage materials,our primary focus is to achieve smooth hydrogen ab-/desorption over a wide temperature range to meet the requirements of fuel cells and their integrated power generation systems.In this paper,the Ti_(0.9)Zr_(0.1)Mn_(1.45)V_(0.4)Fe_(0.15) hydrogen storage alloy was successfully prepared by arc melting.The maximum hydrogen storage capacity reaches 1.89 wt% at 318 K.The alloy has the capability to absorb 90% of hydrogen storage capacity within 50 s at 7 MPa and release 90% of hydrogen within 220 s.Comsol Multiphysics 6.0 software was used to simulate the hydrogen ab-/desorption processes of the tank.The flow rate of cooling water during hydrogen absorption varied in a gradient of(0.02 t x)m s^(-1)(x=0,0.02,0.04,0.06,0.08,0.1,0.12).Cooling water flow rate is positively correlated with the hydrogen absorption rate but negatively correlated with the cost.When the cooling rate is 0.06 m s^(-1),both simulation and experimentation have shown that the hydrogen storage tank is capable of steady hydrogen desorption for over 6 h at a flow rate of 2 L min^(-1).Based on the above conclusions,we have successfully developed a hydrogen-assisted two-wheeler with a range of 80 km and achieved regional demonstration operations in Changzhou and Shaoguan.This paper highlights the achievements of our team in the technological development of fuel cell power generation systems using solid hydrogen storage materials as hydrogen storage carriers and their application in twowheelers in recent years.

Comparative study on the hydrogen storage performance of as-milled MgRENi rapid quenched alloy catalyzed by metal sulfides

The composites of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)as-quenched alloy and 3 wt.%M(M=CoS,CoS_(2),MoS_(2))catalyst were prepared by high-speed vibration ball mill.The effects of metal sulfides on the hydrogenation and dehydrogenation dynamics of alloys were compared.The results show that the as-milled composites contain a large number of amorphous embedded by a small amount of nanocrystals,and there are many point defects.After ball milling,the crystal grain size in the composites containing CoS is relatively larger,followed by CoS_(2)and MoS_(2)again.After hydrogenation,the amorphous phase is crystallized to form Mg_(2)NiH_(4),YH_(3),Pr_(8)H_(18.96),Sm_(3)H_7,Mg,Co or Mo phases,however,Mg_(2)Ni,YH_(2),PrH_(2)and Ni_(3)Y phases appeared after dehydrogenation.The maximum hydrogenation capacity of the composites containing CoS,CoS_(2)and MoS_(2)are 3.939,4.265 and 4.507 wt.%,respectively.The hydrogenation saturation ratio of composite containing MoS_(2)is higher than that of the composites containing CoS and CoS_(2).The dehydrogenation activation energy of the composites containing CoS,CoS_(2)and MoS_(2)is 107.76,68.43 and 63.28 kJ.mol^(-1).H_(2).On the improvement of hydrogen storage performance of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)alloy,the catalytic effect of MoS_(2)sulfide is better than that of CoS_(2)sulfide,and which is better than CoS sulfide.

Properties of Ti-Based Hydrogen Storage Alloy

An efficient and safe hydrogen storage method is one of the important links for the large-scale development of hydrogen in the future. Because of its low price and simple design, Ti-based hydrogen storage alloys are considered to be suitable for practical applications. In this paper, we review the latest research on Ti-based hydrogen storage alloys. Firstly, the machine learning and density functional theory are introduced to provide theoretical guidance for the optimization of Ti-based hydrogen storage alloys. Then, in order to improve the hydrogen storage performance, we briefly introduce the research of AB type and AB2 type Ti-based alloys, focusing on doping elements and adaptive after treatment. Finally, suggestions for the future research and development of Ti-based hydrogen storage alloys are proposed. .

A review of classical hydrogen isotopes storage materials

Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactive tritium.Commonly used HSAs in the hydrogen isotopes field are Zr2M(M=Co,Ni,Fe)alloys,metallic Pd,depleted U,and ZrCo alloy.Specifically,Zr2M(M=Co,Ni,Fe)alloys are considered promising tritium-getter materials,and metallic Pd is utilized to separate and purify hydrogen isotopes.Furthermore,depleted U and ZrCo alloy are well suited for storing and delivering hydrogen isotopes.Notably,all the aforementioned HSAs need to modulate their hydrogen storage properties for complex operating conditions.In this review,we present a comprehensive overview of the reported modification methods applied to the above alloys.Alloying is an effective amelioration method that mainly modulates the properties of HSAs by altering their local geometrical/electronic structures.Besides,microstructural modifications such as nano-sizing and nanopores have been used to increase the specific surface area and active sites of metallic Pd and ZrCo alloys for enhancing de-/hydrogenation kinetics.The combination of metallic Pd with support materials can significantly reduce the cost and enhance the pulverization resistance.Moreover,the poisoning resistance of ZrCo alloy is improved by constructing active surfaces with selective permeability.Overall,the review is constructive for better understanding the properties and mechanisms of hydrogen isotope storage alloys and provides effective guidance for future modification research.

A novel method towards improving the hydrogen storage properties of hypoeutectic Mg-Ni alloy via ultrasonic treatment

Ultrasonic treatment has great contributions on modifying the morphology,dimension and distribution of constituent phases during solidification,which serve as dominate factors influencing the hydrogen storage performance of Mg-based alloys.In this research,ultrasonic treatment is utilized as a novel method to enhance the de-/hydriding properties of Mg-2Ni(at.%)alloy.Due to ultrasonic treatment,the microstructure of as-cast alloy is significantly refined and homogenized.Ascribing to the increased eutectic boundaries and shortened distance insideα-Mg for hydrogen atoms diffusion,the hydrogen uptake capacities and isothermal de-/hydriding rates improve effectively,especially at lower temperature.The peak desorption temperature reduces from 392.99°C to 345.56°C,and the dehydriding activation energy decreases from 101.93 k J mol^(-1)to 88.65 k J mol^(-1).Weakened hysteresis of plateau pressures and slightly optimized thermodynamics are determined from the pressure-composition isotherms.Owing to the refined primary Mg,a larger amount of hydrogen with the higher hydriding proportion is absorbed in the first stage when hydrides nucleate in eutectic region and grow on primary Mg periphery subsequently before MgH2colonies impinging,resulting in the enhancement of hydrogenation rates and capacities.

FeCoNiCrMo high entropy alloy nanosheets catalyzed magnesium hydride for solid-state hydrogen storage

The catalytic effect of FeCoNiCrMo high entropy alloy nanosheets on the hydrogen storage performance of magnesium hydride(MgH_(2))was investigated for the first time in this paper.Experimental results demonstrated that 9wt%FeCoNiCrMo doped MgH_(2)started to dehydrogenate at 200℃and discharged up to 5.89wt%hydrogen within 60 min at 325℃.The fully dehydrogenated composite could absorb3.23wt%hydrogen in 50 min at a temperature as low as 100℃.The calculated de/hydrogenation activation energy values decreased by44.21%/55.22%compared with MgH_(2),respectively.Moreover,the composite’s hydrogen capacity dropped only 0.28wt%after 20 cycles,demonstrating remarkable cycling stability.The microstructure analysis verified that the five elements,Fe,Co,Ni,Cr,and Mo,remained stable in the form of high entropy alloy during the cycling process,and synergistically serving as a catalytic union to boost the de/hydrogenation reactions of MgH_(2).Besides,the FeCoNiCrMo nanosheets had close contact with MgH_(2),providing numerous non-homogeneous activation sites and diffusion channels for the rapid transfer of hydrogen,thus obtaining a superior catalytic effect.

Combined “Gateway” and “Spillover” effects originated from a CeNi_(5) alloy catalyst for hydrogen storage of MgH_(2)

Efficient catalysts enable MgH2 with superior hydrogen storage performance.Herein,we successfully synthesized a catalyst composed of Ce and Ni (i.e.CeNi_(5) alloy) with splendid catalytic action for boosting the hydrogen storage property of magnesium hydride (MgH_(2))The MgH2–5wt%CeNi_(5) composite’s initial hydrogen release temperature was reduced to 174℃ and approximately 6.4wt%H_(2) was released at 275℃ within 10 min.Besides,the dehydrogenation enthalpy of MgH_(2) was slightly decreased by adding CeNi_(5).For hydrogenation,the fully dehydrogenated sample absorbed 4.8wt%H_(2) at a low temperature of 175℃.The hydrogenation apparent activation energy was decreased from(73.60±1.79) to (46.12±7.33) kJ/mol.Microstructure analysis revealed that Mg_(2)Ni/Mg_(2)NiH_(4) and CeH_(2.73) were formed during the process of hydrogen absorption and desorption,exerted combined“Gateway”and“Spillover”effects to reduce the operating temperature and improve the hydrogen storage kinetics of MgH_(2).Our work provides an example of merging“Gateway”and“Spillover”effects in one catalyst and may shed light on designing novel highly-effective catalysts for MgH_(2) in near future.

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.

Direct synthesis of La-Mg-Ni-Co type hydrogen storage alloys from oxide mixtures

(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys were synthesized from the sintered mixture of La;O;+ Ni O + Co O + Mg O in the molten CaCl;electrolyte at 750 °C and the electrochemical hydrogen storage capacities of the synthesized alloys were measured. Non-hygroscopic LaNiO;phase formed during sintering（at 1200 °C for 2 h） as a result of the reaction of hygroscopic La;O;with NiO. Another sinter product was Mg;Ni;O phase. Both mixed oxide sinter products facilitated the La-Ni and Mg-Ni phase formations. X-ray diffraction peaks indicated that the first stable phase appeared in the alloy structure was LaNi;which formed upon reduction of La;NiO;phase. Increase in Mg content caused formation of La;Mg;Ni;phase in the alloy structure and the presence of this phase improved the hydrogen storage performance of the electrodes. It was observed that(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys have promising discharge capacities change between 319 m Ah/g and 379 m Ah/g depending on the alloy Mg content.

Hydrogen storage behavior of nanocrystalline and amorphous La-Mg-Ni-based LaMg_(12)-type alloys synthesized by mechanical milling

Nanocrystalline and amorphous LaMg11Ni+x%Ni(x=100,200,mass fraction)alloys were synthesized by mechanicalmilling.The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system.The gaseous hydrogen absorption and desorption properties were investigated by Sievert’s apparatus and differential scanningcalorimeter(DSC)connected with a H2detector.The results indicated that increasing Ni content significantly improves the gaseousand electrochemical hydrogen storage performances of the as-milled alloys.The gaseous hydrogen absorption capacities andabsorption rates of the as-milled alloys have the maximum values with the variation of the milling time.But the hydrogen desorptionkinetics of the alloys always increases with the extending of milling time.In addition,the electrochemical discharge capacity andhigh rate discharge(HRD)ability of the as-milled alloys both increase first and then decrease with milling time prolonging.

Structure and Electrochemical Properties of A_2B_7-Type La-Mg-Ni Hydrogen Storage Alloys

Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is great, resulting in a linear decrease of the unit cell parameters of main phases and increase of hydrogen absorption/desorption plateau as Mg content increases. Electrochemical measurements show that as the Mg content increases, the discharge capacity of alloy electrodes first increases and then decreases. The cyclic stability presents a deteriorative trend. La1.4Mg0.6 Ni7 alloy electrode exhibits the maximum electrochemical discharge capacity （378 mAh·g^-1）, and the La1.6Mg0.4Ni7 alloy electrode shows the best cyclic stability （S270 = 81%）.

Enhanced hydrogen storage kinetics of nanocrystalline and amorphous Mg_2N-type alloy by substituting Ni with Co

In order to improve the hydrogen storage kinetics of the Mg2Ni-type alloys, Ni in the alloy was partially substituted with element Co. The Mg2Ni-type Mg2Ni1-xCox （x=0, 0.1, 0.2, 0.3, 0.4） alloys were fabricated by melt-spinning technique. The structures of the as-spun alloys were characterized by XRD and TEM. The gaseous and electrochemical hydrogen storage kinetics of the alloys was measured. The results show that the substitution of Co for Ni notably enhances the glass forming ability of the Mg2Ni-type alloy. The amorphization degree of the alloys visibly increases with rising of Co content. Furthermore, the substitution of Co for Ni significantly improves the hydrogen storage kinetics of the alloys. With an increase in the amount of Co substitution from 0 to 0.4, the hydrogen absorption saturation ratio of the as-spun （15 m/s） alloy increases from 81.2% to 84.9%, the hydrogen desorption ratio from 17.60% to 64.79%, the hydrogen diffusion coefficient increases from 1.07×10-11 to 2.79×10-11 cm2/s and the limiting current density increases from 46.7 to 191.7 mA/g, respectively.

Electrochemical hydrogen storage characteristics of nanocrystalline and amorphous Mg_2Ni-type alloys prepared by melt-spinning

The nanocrystalline and amorphous Mg2Ni-type alloys with nominal compositions of Mg2Ni1-xMnx （x=0, 0.1, 0.2, 0.3, 0.4） were synthesized by melt-spinning technique. The spun alloy ribbons with a continuous length, a thickness of about 30 μm and a width of about 25 mm are obtained. The structures of the as-spun alloy ribbons were characterized by XRD and HRTEM. The electrochemical hydrogen storage characteristics of the as-spun alloy ribbons were measured by an automatic galvanostatic system. The electrochemical impedance spectrums （EIS） were plotted by an electrochemical workstation. The hydrogen diffusion coefficients （D） in the alloys were calculated by virtue of potential-step measurement. The results show that all the as-spun （x=0） alloys hold 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 substitution of Mn for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, involving the discharge capacity and the electrochemical cycle stability. With an increase in the amount of Mn substitution from 0 to 0.4, the discharge capacity of the as-spun （20 m/s） alloy increases from 96.5 to 265.3 mA·h/g, and its capacity retaining rate （S20） at the 20th cycle increases from 31.3% to 70.2%. Furthermore, the high rate dischargeability （HRD）, electrochemical impedance spectrum and potential-step measurements all indicate that the electrochemical kinetics of the alloy electrodes first increases then decreases with raising the amount of Mn substitution.

Phase structure and electrochemical properties of La_(0.7)Ce_(0.3)Ni_(3.75)Mn_(0.35)Al_(0.15)Cu_(0.75-x)Fe_x hydrogen storage alloys

La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-xFex （x=0-0.20） hydrogen storage alloys were synthesized by induction melting and subsequent annealing treatment, and phase structure and electrochemical characteristics were investigated. All alloys consist of a single LaNi5 phase with CaCu5 structure, and the lattice constant a and the cell volume （V） of the LaNi5 phase increase with increasing x value. The maximum discharge capacity gradually decreases from 319.0 mA？h/g （x=0） to 291.9 mA？h/g （x=0.20） with the increase in x value. The high-rate dischargeability at the discharge current density of 1200 mA/g decreases monotonically from 53.1% （x=0） to 44.2% （x=0.20）. The cycling stability increases with increasing x from 0 to 0.20, which is mainly ascribed to the improvement of the pulverization resistance.

Electrochemical hydrogen storage characteristics of as-cast and annealed La_(0.8-x)Nd_xMg_(0.2)Ni_(3.15)Co_(0.2)Al_(0.1)Si_(0.05)(x=0-0.4)alloys

The La-Mg-Ni-based A2B7-type La0.8-xNdxMg0.2Ni3.15Co0.2Al0.15 （x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were prepared by casting and annealing. The influences of partial substitution of Nd for La on the structure and electrochemical performance of the as-cast and annealed alloys were investigated. It was found that the experimental alloys consist of two major phases, （La, Mg）2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure, as well as some residual phase LaNi3 and NdNi5. The discharge capacity and high rate discharge ability （HRD） of the as-cast and annealed alloys first increase and then decrease with Nd content growing. The as-cast and annealed alloys （x=0.3） yield the largest discharge capacities of 380.3 and 384.3 mA·h/g, respectively. The electrochemical cycle stability of the as-cast and annealed alloys markedly grows with Nd content rising. As the Nd content increase from 0 to 0.4. The capacity retaining rate （S100） at the 100th charging and discharging cycle increases from 64.98% to 85.17% for the as-cast alloy, and from 76.60% to 96.84% for the as-annealed alloy.

Phase structure and electrochemical properties of La_(1.7+x)Mg_(1.3-x)(NiCoMn)_(9.3)(x=0-0.4) hydrogen storage alloys

The phase structure and electrochemical properties of La1.7＋xMg1.3-x（NiCoMn）9.3（x=0-0.4） alloys were investigated. The XRD analysis reveals that the alloys consist of LaNi5 phase and other phases, such as LaMg2Ni9 phase （PuNi3 structure） and La4MgNi19 phases （Ce5Co19＋Pr5Co19 structure, namely A5B19 type）. With the increase of the x value, the LaMg2Ni9 phase fades away and La4MgNi19 phases appear, while the abundance of LaNi5 phase firstly increases and then decreases. At the same time, the cell volume of LaNi5 phase and LaMg2Ni9 phase decreases. The electrochemical measurement shows that alloy electrodes could be activated in 4-5 cycles, and with the increase of the x value, the maximum discharge capacity gradually increases from 330.9 mA-h/g （x=0） to 366.8 mA-h/g （x=0.4）, but the high-rate dischargeability （HRD） and cyclic stability （S） decrease somewhat （x=0.4, HRD600=82.32%, S100=73.8%）. It is found that the HRD is mainly controlled by the electrocatalytic activity on the alloy electrode surface, and the decline of cyclic stability is due to the appearance of A5B19 type phase with larger hydrogen storage capacity, which leads to larger volume expansion and more intercrystalline stress and then easier pulverization during charging/discharging.

Preparation of ZrMn_2 hydrogen storage alloy by electro-deoxidation in molten calcium chloride

ZrMn2 alloy was electro-synthesized directly from cathode pellets compacted with powdered mixture of MnO2 and ZrO2 in molten calcium chloride. Sintering temperature, cell voltage and electrolysis time were the dominant factors that affected the characteristics of the final product. The results confirmed the formation of pure ZrMn2 alloy through the electro-deoxidation of the mixed oxide pellets at 3.1 V for 12 h in 900 °C CaCl2 melt. The X-ray diffraction（XRD） and cyclic voltammetry analysis suggested that the electro-deoxidation proceeded from the reduction of manganese oxides to Mn, followed by ZrO2 or CaZrO3 reduction on the pre-formed Mn to ZrMn2 alloy. The cyclic voltammetry measurements using powder microelectrode showed that the prepared ZrMn2 alloy has a good electrochemical hydrogen storage property.