Low-Co Lal.8Ti0.2MgNi8.9Co0.1 alloys were prepared by magnetic levitation melting followed by annealing treatment. The effect of annealing on the hydrogen storage properties of the alloys was investigated systematical...Low-Co Lal.8Ti0.2MgNi8.9Co0.1 alloys were prepared by magnetic levitation melting followed by annealing treatment. The effect of annealing on the hydrogen storage properties of the alloys was investigated systematically by X-ray diffraction （XRD）, pressure-com- position isotherm （PCI）, and electrochemical measure- ments. The results show that all samples contain LaNi5 and LaMg2Ni9 phases. LaCo5 phase appears at 1,000 ℃. The enthalpy change of all hydrides is close to -30.6 kJ.mo1-1 H2 of LaNi5 compound. Annealing not only increases hydrogen capacity and improves cycling stability but also decreases plateau pressure at 800 and 900 ℃. After annealing, the contraction of cell volume and the increase of hydride stability cause the high rate dischargeability to reduce slightly. The optimum alloy is found to be one annealed at 900 ℃, with its hydrogen capacity reaching up to 1.53 wt%, and discharge capacity remaining 225.1 mAh·g-1 after 140 charge-discharge cycles.展开更多
TheLa0.5Pr0.2Zr0.1Mg0.2Ni2.75Co0.45Fe0.1Al0.2（M0 and Zr0.65Ti0.35（Mn0.2V0.2Cr0.15Ni0.45）l.76 （M2） hydrogen storage alloys were prepared by inductive melting. In addition, the M1＋30 wt.%M2 composites were success...TheLa0.5Pr0.2Zr0.1Mg0.2Ni2.75Co0.45Fe0.1Al0.2（M0 and Zr0.65Ti0.35（Mn0.2V0.2Cr0.15Ni0.45）l.76 （M2） hydrogen storage alloys were prepared by inductive melting. In addition, the M1＋30 wt.%M2 composites were successively prepared by using high-energy ball milling technology. From the X-ray diffraction （XRD） analysis, it was found that M1 and M2 alloys still retained their respective main phases in the MI＋30 wt.%M2 composites. The scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS） indicated that the decrease in discharge capacity of MI and M2 alloy electrodes was ascribed to the oxidation-dissolution of La, Pr, Mg and Ti, Mn, V, Cr active elements, respectively. The electrochemical studies showed that the M1＋30 wt.%M2 composite electrode ball milling for 5 rain exhibited excellence cyclic stability （92.3%） after 80 charge/discharge cycles, which was higher than 77.7 % and 85.6% of MI and M2 alloy electrodes, respectively. Moreover, at the discharge current density of 1200 mA/g, the high rate dis- charge ability （HRD） of the M1＋30 wt.%M2 composite electrode increased from 61.5% （5 rain） to 70.3% （10 rain）. According to the linear polarization, Tafel polarization and cyclic voltammograms （CV）, the electrochemical kinetics of hydrogen reaction on the sur- face of the electrode and hydrogen diffusion rate in the bulk of alloy were also improved in the ML＋30 wt.%M2composite with in- creasing ball milling time.展开更多
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 di...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 MgzNi phase. La2Mg17 and LaMg2Ni phases decomposed into MgHz, Mg2NiH4 and LaH3 phases during the hydrogenation process. Hydriding/dehydriding measurements indicated that the reversible hydrogen storage capacities of Mg2Ni phase in LaMgs.52Ni2.23M0.15 （M=Cu, Cr） alloys increased to 1.05 wt.% and 0.97 wt.% from 0.79 wt.% of Mg2Ni phase in LaMgs.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.展开更多
In order to improve the overall electrochemical properties of ABs-type storage alloys, the new type composite alloys M1Ni3.5Co0.6Mn0.4Al0.5-x wt% Mm0.89Mg0.11Ni2.97Mn0.14Al0.20Co0.54 （x = 0, 5, 10; M1 means mischmeta...In order to improve the overall electrochemical properties of ABs-type storage alloys, the new type composite alloys M1Ni3.5Co0.6Mn0.4Al0.5-x wt% Mm0.89Mg0.11Ni2.97Mn0.14Al0.20Co0.54 （x = 0, 5, 10; M1 means mischmetal） were prepared by means of ball milling. The composite alloys are shown to be single LaNi5 phase by X-ray diffraction （XRD） patterns. The maximum discharge capacity slightly increases from 315 mAh·g^-1 for M1Ni3.5Co0.6Mn0.4Al0.5 to 324 mAh·g^-1 （x = 5） and 325 mAh·g^-1 （x = 10）. The addition of AB3-type La-Mg- Ni-based alloy has a positive effect on the cycle stability. With the addition of Mm0.89Mg0.11Ni2.97Mn0.14-Al0.20Co0.54 alloy, the exchange current density （I0）, the limiting current density （IL） and the diffusion coefficient of hydrogen （D） of the alloy electrodes increase, leading to a corresponding improvement of the high rate dischargeability.展开更多
采用真空感应熔炼法制备了La0.82Mg0.18Ni3.5-xAlx（x=0.05~0.20）四元储氢合金,并在四氢呋喃作用下对合金进行机械合金化改性。考察了球磨时间和四氢呋喃用量对合金电化学性能及其表面及体相内电阻的作用机制。通过3因素4水平正交实验...采用真空感应熔炼法制备了La0.82Mg0.18Ni3.5-xAlx（x=0.05~0.20）四元储氢合金,并在四氢呋喃作用下对合金进行机械合金化改性。考察了球磨时间和四氢呋喃用量对合金电化学性能及其表面及体相内电阻的作用机制。通过3因素4水平正交实验确定最佳的球磨参数以及Al的最佳替代量。结果表明合金相结构以La Ni5相和La2Ni7相为主,随着Al替代量的增加和四氢呋喃用量的减少,La2Ni7相逐渐减少,La Ni5相逐渐增多,晶胞参数和晶胞体积增大。电化学性能的循环稳定性有大幅提升,但放电比容量呈降低趋势,从356.2 m Ah/g降到339.3 m Ah/g;电化学交流阻抗频谱（EIS）和线性极化测试结果表明合金表面的电荷迁移随着Al含量的增加逐渐下降;而合金体相内氢扩散速率先降低后上升再降低,整体呈降低趋势,高倍率放电能力主要由合金体内氢扩散控制。展开更多
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 di...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.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.51071054 and51271061)the Natural Science Foundation of Guangxi(Nos.2010GXNSFD013004 and 2012GXNSFBA053149)
文摘Low-Co Lal.8Ti0.2MgNi8.9Co0.1 alloys were prepared by magnetic levitation melting followed by annealing treatment. The effect of annealing on the hydrogen storage properties of the alloys was investigated systematically by X-ray diffraction （XRD）, pressure-com- position isotherm （PCI）, and electrochemical measure- ments. The results show that all samples contain LaNi5 and LaMg2Ni9 phases. LaCo5 phase appears at 1,000 ℃. The enthalpy change of all hydrides is close to -30.6 kJ.mo1-1 H2 of LaNi5 compound. Annealing not only increases hydrogen capacity and improves cycling stability but also decreases plateau pressure at 800 and 900 ℃. After annealing, the contraction of cell volume and the increase of hydride stability cause the high rate dischargeability to reduce slightly. The optimum alloy is found to be one annealed at 900 ℃, with its hydrogen capacity reaching up to 1.53 wt%, and discharge capacity remaining 225.1 mAh·g-1 after 140 charge-discharge cycles.
基金supported by the Natural Science Foundation of Guangxi (2011GXNSFA018034)the Program for Characteristic Professionalism and Integrated Curriculum Construction in Colleges of Guangxi (GXTSZY024)
文摘TheLa0.5Pr0.2Zr0.1Mg0.2Ni2.75Co0.45Fe0.1Al0.2（M0 and Zr0.65Ti0.35（Mn0.2V0.2Cr0.15Ni0.45）l.76 （M2） hydrogen storage alloys were prepared by inductive melting. In addition, the M1＋30 wt.%M2 composites were successively prepared by using high-energy ball milling technology. From the X-ray diffraction （XRD） analysis, it was found that M1 and M2 alloys still retained their respective main phases in the MI＋30 wt.%M2 composites. The scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS） indicated that the decrease in discharge capacity of MI and M2 alloy electrodes was ascribed to the oxidation-dissolution of La, Pr, Mg and Ti, Mn, V, Cr active elements, respectively. The electrochemical studies showed that the M1＋30 wt.%M2 composite electrode ball milling for 5 rain exhibited excellence cyclic stability （92.3%） after 80 charge/discharge cycles, which was higher than 77.7 % and 85.6% of MI and M2 alloy electrodes, respectively. Moreover, at the discharge current density of 1200 mA/g, the high rate dis- charge ability （HRD） of the M1＋30 wt.%M2 composite electrode increased from 61.5% （5 rain） to 70.3% （10 rain）. According to the linear polarization, Tafel polarization and cyclic voltammograms （CV）, the electrochemical kinetics of hydrogen reaction on the sur- face of the electrode and hydrogen diffusion rate in the bulk of alloy were also improved in the ML＋30 wt.%M2composite with in- creasing ball milling time.
基金Project supported by High-Tech Research and Development(863)Program of China(2007AA05Z117)National Natural Science Foundation of China(50971112,51171165)the Natural Science Foundation of Hebei Province(E201001170)
文摘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 MgzNi phase. La2Mg17 and LaMg2Ni phases decomposed into MgHz, Mg2NiH4 and LaH3 phases during the hydrogenation process. Hydriding/dehydriding measurements indicated that the reversible hydrogen storage capacities of Mg2Ni phase in LaMgs.52Ni2.23M0.15 （M=Cu, Cr） alloys increased to 1.05 wt.% and 0.97 wt.% from 0.79 wt.% of Mg2Ni phase in LaMgs.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.
基金the National Natural Science Foundation of China(51071054,50861003)the Natural Science Foundation of Guangxi(2010GXNSFD013004)+2 种基金the Foundation of Key Laboratory of National Education Ministry for Nonferrous Metals and Materials Processing Technology(GXKFJ09-15)the Guangxi University Program for Science and Technology Research(XBZ110379)the Innovation Team Project of Guangxi University
基金financially supported by the National Natural Science Foundation of China(No.11364013)Guangxi Scientific Experiment Center of Mining,Metallurgy and Environment Foundation of Guilin University of Technology(No.KH2012YB002)+1 种基金the Education Department and Scientific Foundation of Guangxi(No.201203YB088)the Students Innovative and Undertaking Projects of Guangxi(No.2013HSCX002)
文摘In order to improve the overall electrochemical properties of ABs-type storage alloys, the new type composite alloys M1Ni3.5Co0.6Mn0.4Al0.5-x wt% Mm0.89Mg0.11Ni2.97Mn0.14Al0.20Co0.54 （x = 0, 5, 10; M1 means mischmetal） were prepared by means of ball milling. The composite alloys are shown to be single LaNi5 phase by X-ray diffraction （XRD） patterns. The maximum discharge capacity slightly increases from 315 mAh·g^-1 for M1Ni3.5Co0.6Mn0.4Al0.5 to 324 mAh·g^-1 （x = 5） and 325 mAh·g^-1 （x = 10）. The addition of AB3-type La-Mg- Ni-based alloy has a positive effect on the cycle stability. With the addition of Mm0.89Mg0.11Ni2.97Mn0.14-Al0.20Co0.54 alloy, the exchange current density （I0）, the limiting current density （IL） and the diffusion coefficient of hydrogen （D） of the alloy electrodes increase, leading to a corresponding improvement of the high rate dischargeability.
文摘采用真空感应熔炼法制备了La0.82Mg0.18Ni3.5-xAlx（x=0.05~0.20）四元储氢合金,并在四氢呋喃作用下对合金进行机械合金化改性。考察了球磨时间和四氢呋喃用量对合金电化学性能及其表面及体相内电阻的作用机制。通过3因素4水平正交实验确定最佳的球磨参数以及Al的最佳替代量。结果表明合金相结构以La Ni5相和La2Ni7相为主,随着Al替代量的增加和四氢呋喃用量的减少,La2Ni7相逐渐减少,La Ni5相逐渐增多,晶胞参数和晶胞体积增大。电化学性能的循环稳定性有大幅提升,但放电比容量呈降低趋势,从356.2 m Ah/g降到339.3 m Ah/g;电化学交流阻抗频谱（EIS）和线性极化测试结果表明合金表面的电荷迁移随着Al含量的增加逐渐下降;而合金体相内氢扩散速率先降低后上升再降低,整体呈降低趋势,高倍率放电能力主要由合金体内氢扩散控制。
基金Project supported by the National Natural Science Foundation of China(50642033 50701011)+1 种基金Key Technologies R&D Program of Inner Mongolia, China (20050205)Natural Science Foundation of Inner Mongolia, China (200711020703)
文摘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.
