Structure and electrochemical hydrogen storage characteristics of the as-cast and annealed La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 （x=0-0.4） alloys

In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4) elec-trode alloys were fabricated by casting and annealing. The microstructures of the as-cast and annealed alloys were characterized by XRD and SEM. The electrochemical hydrogen storage characteristics of the as-cast and annealed alloys were measured. The results revealed that all of the experimental alloys mainly consisted of two phases: (La,Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. As Sm content grew from 0 to 0.4, the discharge capacity and the high rate discharge ability (HRD) first in-creased and then decreased for the as-cast and annealed alloys, whereas the capacity retaining rate (S100) after 100 cycles increased continuously.     

Effect of annealing temperature on microstructure and electrochemical performance of La0.75Mg0.25Ni3.5Co0.2 hydrogen storage electrode alloy

To improve the cyclic stability of La-Mg-Ni system alloy, as-cast La0.75Mg0.25Ni3.5Co0.2 alloy was annealed at 1123, 1223, and 1323 K for 10 h in 0.3 MPa argon. The microstructure and electrochemical performance of different annealed alloys were investigated systematically by X-Ray Diffraction （XRD）, Scanning Electron Microscopy （SEM）, X-Ray Photoelectron Spectroscopy （XPS）, and electrochemical experiments. The results obtained by XRD and SEM showed that the as-cast and annealed （1123 K） alloys had multiphase structure containing LaNis, （La, Mg）2（Ni, Co）7 and few LaNi2 phases. When annealing temperatures approached 1223 and 1323 K, LaNi2 phase disappeared. The annealed alloys at 1223 and 1323 K were composed of LaNi5, （La, Mg）2（Ni, Co）7 and （La, Mg）（Ni, Co）3 phases. With increasing annealing temperature, the maximum discharge capacity of the alloy decreased monotonously, but the cyclic stability was improved owing to structure homogeneity and grain growth after annealing, as well as the enhancement of anti-oxidation/corrosion ability and the suppression of pulverization during cycling in KOH electrolyte.     

Effect of annealing treatment on hydrogen storage properties of La-Ti-Mg-Ni-based alloy

The present study dealt with investigations on the effects of annealing on the hydrogen storage properties of La 1.6 Ti 0.4 MgNi 9 alloys.The experimental alloys were prepared by magnetic levitation melting followed by annealing treatment.For La 1.6 Ti 0.4 MgNi 9 alloys,LaNi 5,LaNi 3 and LaMg 2 Ni 9 were the main phases,Ti 2 Ni phase appeared at 900℃.Annealing not only enhanced the maximum and effective hydrogen storage capacity,improved the hydrogen absorption/desorption kinetics,but also increased the discharge capacity.The cyclic stability had been improved markedly by annealing,e.g.,when the discharge capacity reduced to 60% of maximum discharge capacity,the charge/discharge cycles increased from 66(as-cast) to 89(annealed at 800℃) and 127 times(annealed at 900℃).La 1.6 Ti 0.4 MgNi 9 alloy annealed at 900℃ exhibited better electrochemical properties compared to the other two alloy electrodes.     

Effect of the partial substitution of samarium for lanthanum on the structure and electrochemical properties of La_(15)Fe_(77)B_8-type hydrogen storage alloys

La15Fe77B8 hydrogen storage alloys were prepared using a vacuum induction-quenching furnace. The results of X-ray diffraction(XRD) and scanning electron microscopy(SEM) suggested that La15–xSmxFe2Ni76Mn5B2(x=0, 2, 4, 6) alloys had multiphase structure including the main LaNi5 phase, La3Ni13B2 phase and(Fe, Ni) phase. With the increasing substitution of Sm for La, the main phase structure of alloys did not change, while the unit cell volumes decreased, the cycle stability was improved and the maximum discharge capacity decreased, but the low temperature maximum discharge capacity of the same substitution alloy was gradually approaching the maximum discharge capacity at room temperature, which showed that La15Fe77B8 hydrogen storage alloys of the partial substitution of Sm for La had better low-temperature dischargeability(LTD). For the same substitution alloys, self-discharge characteristics and cycle stability at low temperature were better than that at room temperature. Furthermore, the high-rate dischargeability(HRD) and the exchange current density I0 first increased and then decreased with the increasing of Sm content, whereas the hydrogen diffusion coefficient D in alloy bulk decreased gradually, which indicated that appropriate substitution of Sm for La improved the electrochemical kinetics properties of the alloys. The HRD was mainly dominated by the charge-transfer rate on the alloy surface.     

Study on structure and electrochemical properties of the （LaGdMg）Ni3.35-xCoxAl0.15（x=0-2.0） hydrogen storage alloys

Hydrogen storage alloys(LaGdMg)Ni3.35-xCoxAl0.15(x=0,0.1,0.3,0.5,1.0,1.5,2.0) were prepared by induction melting followed by annealing treatment in argon atmosphere.The effects of partly replacing Ni by Co element in(LaGdMg)Ni3.35Al0.15 on the phase structure and electrochemical properties of(LaGdMg)Ni3.35-xCoxAl0.15 alloys were investigated.Structure analysis showed that the alloys consisted of Ce2Ni7-type(Gd2Co7-type),CaCu5-type,Pr5Co19-type,PuNi3-type phase structure.The addition of Co element obviously reduced the contents of CaCu5-type phase and increased the contents of Ce2Ni7-type phase.However,Pr5Co19-type and CaCu5-type phase obviously increased with the high content of Co.Rietveld analysis showed that the c-axis lattice parameters and cell volumes of the component phases increased with increasing Co content.The electrochemical measurements showed that as the Co content increased,the maximum discharge capacity and the cyclic stability of the annealed alloys both first increased then decreased.The(LaGdMg)Ni3.05Co0.3Al0.15 alloy electrode exhibited the maximum discharge capacity(392.92 mAh/g),and the(LaGdMg)Ni1.85Co1.0Al0.15 alloy electrode showed the best cyclic stability(S100=96.1%).     

Influence of melt spinning and annealing treatment on structures and hydrogen storage thermodynamic properties of La0.8Pr0.2MgNi3.6Co0.4 alloy

La0.8Pr0.2MgNi3.6Co0.4 alloys were prepared by induction melting,annealing and melt spinning techniques.The influences of annealing treatment and melt spinning on phase structure and hydrogen storage properties were systematically investigated.The results of X-ray diffraction determine that the as-cast and as-spun La0.8Pr0.2MgNi3.6Co0.4 alloys consist of LaMgNi4 and LaNi5 phases,while only LaMgNi4 phase is present in the as-annealed alloy.The scanning electron microscope images illustrate that the grain of the alloy is significantly refined by melt spin ning tech no logy.The gaseous hydrogen storage kinetic and thermodynamic properties were measured by using a Sievert's apparatus at different temperatures.The maximum hydrogen storage capacity of the as-cast,as?spun and as-annealed La0.8Pr0.2MgNi3.6Co0.4 alloy is 1.699,1.637 and 1.535 wt.% at 373 K and 3 MPa,respectively.The annealed alloy has flatter and wider pressure plateaus compared with the as-cast and as-spun alloys,which correspond to the hydrogen absorption and desorption process of LaMgNi4 and corresponding hydride.Furthermore,the enthalpy and entropy changes of LaMgNi4 during hydrogenation at different temperatures were calculated using Van't Hoff methods.     

Phase,microstructure, and magnetocaloric effect of the large disc LaFe11.6Si1.4 alloy

The large disc LaFe11.6Si1.4 alloy, which was prepared by medium-frequency induction furnace, was annealed at 1503 K for different time. The main phases were 1:13 phase in the edge parts of the large discs alloy; the impurity phases included α-Fe phase, LaFeSi phase, and even very small amount of La5Si3 phase. The amounts of impurity phases reduced with increasing in annealing time. The magnetic properties in the edge parts of the large discs LaFe11.6Si1.4 alloy were investigated. The magnetic susceptibility had an abrupt change at Curie temperature(TC) as the magnetization in M-T curves. The alloys had almost the same TC(191 K), the magnetocaloric effect(MCE) and relative cooling power(RCP) increased with increasing in annealing time. In addition, for the same alloy, the magnetic hysteresis decreased with the increase in temperature.     

Effect of Rapid Quenching on Microstructures and Electrochemical Performances of La2Mg（Ni0.85Co0.15）9M0.1 （M = B, Cr） Hydrogen Storage Alloys

The La-Mg-Ni-system （PuNi3-type） La2Mg （Ni0.85 Co0.15 ）9M0.1 （ M = B, Cr） hydrogen storage etectrode alloys were prepared by casting and rapid quenching. The electrochemical performances and microstructures of the as-cast and quenched alloys were determined and measured. The effects of rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The obtained results show that the alloys are composed of the （La, Mg） Ni3 phase （PuNi3-type structure） and the LaNi5 phase, as well as the small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast alloy containing boron, and the Ni2B phase in the alloy nearly disappears after rapid quenching. The relative amount of each phase in the alloys depends on the quenching rate. The rapid quenching technique can greatly improve the electrochemical performance of the alloy, and the effect of rapid quenching on the activation performances of the alloys is minor. Rapid quenching enhances the cycle stability of the alloy, and the cycle life of the alloy increases with the increase of the quenching rate.     

Effect of annealing treatment on the anti-pulverization and anti-corrosion properties of La0.67Mg0.33Ni2.5Co0.5 hydrogen storage alloy

The La0.67Mg0.33Ni2.5Co0.5 hydrogen storage alloy was prepared by the vacuum intermediate frequency induction furnace followed by annealing treatment. The pulverization degree of both the as-cast and annealed alloy powders after gaseous hydriding and dehydriding cycle was investigated and the discovery was that annealing treatment could hardly ameliorate their anti-pulverization ability. The element content of La, Mg, Ni and Co existing in electrolyte before and after the electrochemical cycles by using ICP-AES technology was also analyzed and it showed that a large amount of La and Mg were dissolved in the electrolyte, but the amount of dissolution for La and Mg significantly declined when the alloy was annealed. The XRD analysis revealed that all the alloys consisted of two main phases AB3 and AB2 and a residual phase AB5 while annealing treatment made the AB2 phase decrease slightly. Furthermore, the anti-corrosion abilities of various elements in different phases of the as-cast and annealed alloy samples were studied by analyzing the element(La, Mg, Ni, Co) change with the corrosion time in phases AB3 and AB2 by means of EDS. It turned out that the element of La was mainly corroded out from the phase AB2 while not easily from the phase AB3. However, the element of Mg was both easily corroded out from the phases AB2 and AB3, but the corrosion was more obvious in the phase AB3. Therefore, annealing improved the anti-corrosion performances of La and Mg in the phase AB2.     

Investigations on hydrogen storage properties of LaMg8.52Ni2.23M0.15 （M=Ni, Cu, Cr） alloys

LaMg8.52Ni2.23M0.15 (M=Ni, Cu, Cr) alloys were prepared by induction melting. X-ray diffraction showed that all the three alloys had a multiphase structure, consisting of La2Mg17, LaMg2Ni and Mg2Ni phases. Energy dispersive X-ray spectrometer results revealed that most of Cu and Cr distributed in Mg2Ni phase. La2Mg17 and LaMg2Ni phases decomposed into MgH2, Mg2NiH4 and LaH3 phases during the hydrogenation process. Hydriding/dehydriding measurements indicated that the reversible hydrogen storage capacities of Mg2Ni phase in LaMg8.52Ni2.23M0.15 (M=Cu, Cr) alloys increased to 1.05 wt.% and 0.97 wt.% from 0.79 wt.% of Mg2Ni phase in LaMg8.52Ni2.38 alloy at 523 K. Partial substitution of Cu and Cr for Ni decreased the onset dehydrogenation temperature of the alloy hydrides and the temperature lowered by 18.20 and 5.50 K, respectively. The improvement in the dehydrogenation property of the alloys was attributed to that Cu and Cr decreased the stability of Mg2NiH4 phase.     

熔炼次数对M17返回料合金成分、组织和性能的影响

实验结果表明,M17铸造高温合金(%:0.16C、8.79Cr、5.79A1、4.93Ti、3.29Mo、15.20Co、0.78V、0.015B、0.073Zr、0.002S、0.001P、0.001 1O、0.001 0N)经25 kg真空感应炉返回重熔后,Si含量随重熔次数的增加而略有增加,合金中主要元素和其它杂质元素S、P、H的含量变化不大,而氧、氮略有增加;合金中初生碳化物由新合金中的草书体逐渐向返回合金块状转变,初生碳化物的遗传性堵塞合金凝固时的补缩通道,使返回料合金的疏松倾向增大,高温塑性下降较大。     

China's Major Non-ferrous Metals Imports & Exports

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Zinc Production by Province in 2014

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80% of Chinese Firms Purchasing Overseas Mines Ended up in the Red

<正>Minmetals Resources acquired the world’s largest copper mine under construction for USD5.85 billion.One after another,listed companies Jien Nickle,China Molybdenum and Chihong Zinc and Germanium raised money to get involved in overseas mining projects…SOEs and private enterprises are engaged in a frenzy of overseas mine purchasing.A reporter with Economic     

Copper Processing Profit Dropped Sharply,Copper Consumption Will Face Impact in the Second Half of the Year

正Judging from China’s copper consumption field,the biggest consumption unit is electric power,which accounts for 47%of total consumption;it is followed by light industry sector,including household electrical appliance,machinery,durable goods and hardware etc,which accounts for 22%of total consumption;followed by transportation field,     

Central Geological Prospecting Fund Newly Added 16.47 Million Tonnes of Bauxite in 2013

正In 2013,the Central Geological Prospecting Fund(CGPF)Project newly discovered 15 ore fields,including 3 large above ore fields,and 5medium sized ore fields.The reporter learned from the recently published"Annual Report of Central Geological Prospecting Fund Project(2013)"that,from 2006 to 2013 the CGPF     

Manufacturers of Copper Tube for Central Air Conditioner Use Face Mounting Pressure in the Final Quarter of the Year

正This year,the investment growth rate of real estate industry continued to slow down,sold area of commercial housing also dropped significantly,which brought huge pressure to the domestic air conditioning manufactures.In the first half of the year,by relying on high growth in national financial expenditure,along with investment in public infrastructure     

Xinjiang Ranks No.1 in Production of Primary Aluminum in China

正Kang Yi,Honorary Chairman of China Nonferrous Metals Industry Association,said recently at the Forum on Development of the Non-ferrous Metals Industry in Central and Western China held in Zhengzhou that,as more and more electrolytic aluminum factories in Xinjiang came into operation,the electrolytic aluminum output of Xinjiang had reached2,275,000 tons in the first 7 months this year,     

Shenhuo Coal Industry and Electricity Power Completed800,000 t/a Aluminum Project in Xinjiang

正"Xinjiang project has been completed according to schedule,but total completion and total start of production are two different concepts,after completion it still needs a gradual process of reaching production target."On the morning of November 3,Shenhuo Coal Industry and Electricity Power told investors the above statement on the investor interaction platform.     

Guangdong Metal Transaction Center has Become the Second Largest Precious Metal Transaction Platform Nationwide

正The reporter learned from Guangdong Province Precious Metal Transaction Center that in 2013the Center maintained healthy development momentum,and had become the second largest precious metal transaction platform in China in terms of market size;currently Guangdong is quickening steps of financial innovation for the Center,aiming to build a transaction center with international core competitiveness.