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 inves...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.展开更多
Hydrogen storage composite alloy Ti0.10Zr0.15V0.35Cr0.10Ni0.30–10% LaNi3 was prepared by two-step arc-melting to improve the electro-catalytic activity and the kinetic performance of Ti-V-based solid solution alloy. ...Hydrogen storage composite alloy Ti0.10Zr0.15V0.35Cr0.10Ni0.30–10% LaNi3 was prepared by two-step arc-melting to improve the electro-catalytic activity and the kinetic performance of Ti-V-based solid solution alloy. The electrochemical properties and synergetic effect of the composite alloy electrode were systematically investigated by using X-ray diffractometry, field emission scanning electron microscopy, energy-dispersive spectrometry, electrochemical impedance spectroscopy and galvanostatic charge/discharge test. It is found that the main phase of the composite alloy is composed of V-based solid solution phase with a BCC structure and C14 Laves phase with hexagonal structure, while the secondary phase is formed in the composite alloy. The comprehensive electrochemical properties of the composite alloy electrode are significantly improved. The activation cycle number, the maximum discharge capacity and the low temperature dischargeability of the composite alloy are 5 cycles, 362.5 mA-h/g and 65.84% at 233 K, respectively. It is suggested that distinct synergetic effect occurs in the activation process, composite process, cyclic process and discharge process at a low or high temperature under different current densities, in the charge–transfer resistance and exchange current density.展开更多
The LaMgNi4xCox （x=0, 0.3, 0.5） compounds were prepared by the method of levitation melting and a subsequent heat treatment at 1073 K for 10 h. XRD analysis shows that the obtained LaMgNia-xCox alloys consist of a s...The LaMgNi4xCox （x=0, 0.3, 0.5） compounds were prepared by the method of levitation melting and a subsequent heat treatment at 1073 K for 10 h. XRD analysis shows that the obtained LaMgNia-xCox alloys consist of a single phase with the structure of cubic SnMgCu4 （AuBe5 type）. The hydrogen absorption/desorption properties of LaMgNi4 were investigated by PCI measurement at various temperatures （T=373, 398, 423 K） and the results show that the maximum absorbed hydrogen capacity reaches 1.45% （5.79H/M） under a hydrogen pressure of 4.3 MPa at 373 K. The XRD patterns during absorbing procedure at 373 K indicate the phase structure changing from cubic （a-LaMgNi4） to orthorhombic （fl-LaMgNiaH3.41） and after hydrogenation finally back to cubic （y-LaMgNiaH4.87）, and a partial desorption was also observed under this condition. With increasing temperature, a slight decrease of the absorbed hydrogen content was observed and the number of plateaus reduces from two to one, but the hydrogen absorption kinetics improves. The electrochemical properties of the LaMgNiaxCox were measured by simulated battery test, which shows that the discharge capacity of the alloys significantly improves with the increase of Co content.展开更多
Anodic electrodes with the mixture of hydrogen storage alloys and different contents of Co3O4（2%,4%,6% and 8%,mass fraction） powders were made.The effects of Co3O4 on the electrochemical performance of the alloy ele...Anodic electrodes with the mixture of hydrogen storage alloys and different contents of Co3O4（2%,4%,6% and 8%,mass fraction） powders were made.The effects of Co3O4 on the electrochemical performance of the alloy electrodes were studied.The constant charge-discharge tests show that the discharge capacity of alloy electrodes with Co3O4 significantly increases,and the maximum discharge capacities of electrodes with 2%,4%,6% and 8% Co3O4 are higher than the electrode with no Co3O4 by 0.83%,4.86%,7.18% and 9.21%,accordingly.Linear polarization（LP） and electrochemical impedance spectroscopy（EIS） tests suggest that charge-transfer resistance decreases by the addition of Co3O4.Cyclic voltammogram（CV）,scanning electron microscopy（SEM） and energy dispersive spectrum（EDS） tests indicate that Co3O4 can partly dissolve and experience a reversible oxidation-reduction process of Co to Co（OH）2,leading to the improvement in the electrochemical performance of hydrogen storage alloy.展开更多
For the purpose of improving the electrochemical cycle stability of the La-Mg-Ni based A2BT-type electrode alloys, both reducing Mg content and substituting La with Pr were adopted. The Lao.8-xPrxMg0.2Ni3.15Co0.2A10.1...For the purpose of improving the electrochemical cycle stability of the La-Mg-Ni based A2BT-type electrode alloys, both reducing Mg content and substituting La with Pr were adopted. The Lao.8-xPrxMg0.2Ni3.15Co0.2A10.1Si0.05 （x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were fabricated by casting and annealing. The investigation on the structures and electrochemical performances of the alloys was performed. The obtained results reveal that the as-cast and annealed alloys comprise two major phases, （La, Mg）2Ni7 phase with the hexagonal Ce2NiT-type structure and LaNi5 phase with the hexagonal CaCus-type structure, as well as a little residual LaNi3 phase. It is also found that the addition of Pr element observably affects the electrochemical hydrogen storage characteristics of the alloys, just as the discharge capacity and high rate discharge ability （HRD） first rise then fall with the growing of Pr content, and among all the alloys, the as-cast and annealed （x=0.3） alloys generate the largest discharge capacities of 360.8 and 386.5 mA.h/g, respectively. Additionally, the electrochemical cycle stability of all the alloys markedly grows with the increase of Pr content. The capacity retaining rate （S100） at the 100th charging and discharging cycle is enhanced from 64.98% to 77.55% for the as-cast alloy, and from 76.60% to 95.72% for the as-annealed alloy by rising Pr content from 0 to 0.4. Furthermore, the substitution of Pr for La results in first increase and then decrease in the hydrogen diffusion coefficient （D）, the limiting current density （IL） as well as the electrochemical impedance.展开更多
A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys...A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys were characterized by XRD,EDS and SEM to investigate the effects of B and Fe substitution for Ni on material structure.The content of LaMg2Ni9 phase within La0.7Mg0.3Ni3 alloy reaches 37.9% and that of La0.7Mg0.3Ni2.9(FeB)0.1 alloys reduces to 23.58%.Among all samples,ground particles with different shapes correspond to different phases.The major substitution occurs in LaMg2Ni9 phase.Electrochemical tests indicate that substituted alloys have different electrochemical performance,which is affected by phase structures of alloy.The discharge capacity of La0.7Mg0.3Ni3 alloy reaches 337.3 mA·h/g,but La0.7Mg0.3Ni2.9(FeB)0.1 alloy gets better high rate discharge(HRD) performance at the discharge rate of 500 mA/g with a high HRD value of 73.19%.展开更多
The Co-S/x wt.% AB5 （x=0, 10, 20, 30） composite materials were prepared by simply mixing Co-S material fabricated by hy- drothermal method and AB5 alloy. The structure and morphology of the composite materials were ...The Co-S/x wt.% AB5 （x=0, 10, 20, 30） composite materials were prepared by simply mixing Co-S material fabricated by hy- drothermal method and AB5 alloy. The structure and morphology of the composite materials were characterized by XRD and SEM, respectively. The electrochemical properties of the composite electrodes were studied by the galvanostatic charge, dis- charge test and electrochemical impedance spectroscopy. The results showed that the Co-S/20 wt.% AB5 composite electrode showed the highest discharge capacity and the best cycling stability. The existence of the AB5 alloy improved the electro- chemical activity of composite electrodes, reduced the electrochemical polarization resistances and promoted the electrochem- ical conversion reaction between Co and Co（OH）2. In order to improve the utilization rate of active materials, 0.0! mol/L Na2S203 was added into the electrolyte. The electrochemical properties of the composite electrode were significantly enhanced. After fifty cycles, the discharge capacity of the composite electrode increased from 407 to 481.7 mAh/g and the capacity reten- tion increased from 79.7% to 91.2%.展开更多
基金Project (51001043) supported by the National Natural Science Foundation of ChinaProject (NCET2011) supported by Program for New Century Excellent Talents in University, China+4 种基金Project (201104390) supported by China Postdoctoral Science Special FoundationProject (20100470990) supported by China Postdoctoral Science FoundationProject (2012IRTSTHN007) supported by Program for Innovative Research Team (in Science and Technology) in the University of Henan Province, ChinaProject (2011J1003) supported by Baotou Science and Technology Project, ChinaProject (B2010-13) supported by the Doctoral Foundation of Henan Polytechnic University, China
文摘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.
基金Project (B2011203074) supported by the Natural Science Foundation of Hebei Province, ChinaProject (201101A129) supported by the Technology Research and Development Program of Qinhuangdao, Hebei Province, China
文摘Hydrogen storage composite alloy Ti0.10Zr0.15V0.35Cr0.10Ni0.30–10% LaNi3 was prepared by two-step arc-melting to improve the electro-catalytic activity and the kinetic performance of Ti-V-based solid solution alloy. The electrochemical properties and synergetic effect of the composite alloy electrode were systematically investigated by using X-ray diffractometry, field emission scanning electron microscopy, energy-dispersive spectrometry, electrochemical impedance spectroscopy and galvanostatic charge/discharge test. It is found that the main phase of the composite alloy is composed of V-based solid solution phase with a BCC structure and C14 Laves phase with hexagonal structure, while the secondary phase is formed in the composite alloy. The comprehensive electrochemical properties of the composite alloy electrode are significantly improved. The activation cycle number, the maximum discharge capacity and the low temperature dischargeability of the composite alloy are 5 cycles, 362.5 mA-h/g and 65.84% at 233 K, respectively. It is suggested that distinct synergetic effect occurs in the activation process, composite process, cyclic process and discharge process at a low or high temperature under different current densities, in the charge–transfer resistance and exchange current density.
基金Projects(10JC407700,11ZR1417600) supported by the Science and Technology Committee of Shanghai,ChinaProject(12ZZ017) supported by the Shanghai Education Commission,China
文摘The LaMgNi4xCox （x=0, 0.3, 0.5） compounds were prepared by the method of levitation melting and a subsequent heat treatment at 1073 K for 10 h. XRD analysis shows that the obtained LaMgNia-xCox alloys consist of a single phase with the structure of cubic SnMgCu4 （AuBe5 type）. The hydrogen absorption/desorption properties of LaMgNi4 were investigated by PCI measurement at various temperatures （T=373, 398, 423 K） and the results show that the maximum absorbed hydrogen capacity reaches 1.45% （5.79H/M） under a hydrogen pressure of 4.3 MPa at 373 K. The XRD patterns during absorbing procedure at 373 K indicate the phase structure changing from cubic （a-LaMgNi4） to orthorhombic （fl-LaMgNiaH3.41） and after hydrogenation finally back to cubic （y-LaMgNiaH4.87）, and a partial desorption was also observed under this condition. With increasing temperature, a slight decrease of the absorbed hydrogen content was observed and the number of plateaus reduces from two to one, but the hydrogen absorption kinetics improves. The electrochemical properties of the LaMgNiaxCox were measured by simulated battery test, which shows that the discharge capacity of the alloys significantly improves with the increase of Co content.
基金Projects(21071153,20976198)supported by the National Natural Science Foundation of China
文摘Anodic electrodes with the mixture of hydrogen storage alloys and different contents of Co3O4（2%,4%,6% and 8%,mass fraction） powders were made.The effects of Co3O4 on the electrochemical performance of the alloy electrodes were studied.The constant charge-discharge tests show that the discharge capacity of alloy electrodes with Co3O4 significantly increases,and the maximum discharge capacities of electrodes with 2%,4%,6% and 8% Co3O4 are higher than the electrode with no Co3O4 by 0.83%,4.86%,7.18% and 9.21%,accordingly.Linear polarization（LP） and electrochemical impedance spectroscopy（EIS） tests suggest that charge-transfer resistance decreases by the addition of Co3O4.Cyclic voltammogram（CV）,scanning electron microscopy（SEM） and energy dispersive spectrum（EDS） tests indicate that Co3O4 can partly dissolve and experience a reversible oxidation-reduction process of Co to Co（OH）2,leading to the improvement in the electrochemical performance of hydrogen storage alloy.
基金Projects(51161015,50961009) supported by the National Natural Science Foundation of ChinaProject(2011AA03A408) supported by the National High Technology Research and Development Program of ChinaProjects(2011ZD10,2010ZD05) supported by the Natural Science Foundation of Inner Mongolia,China
文摘For the purpose of improving the electrochemical cycle stability of the La-Mg-Ni based A2BT-type electrode alloys, both reducing Mg content and substituting La with Pr were adopted. The Lao.8-xPrxMg0.2Ni3.15Co0.2A10.1Si0.05 （x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were fabricated by casting and annealing. The investigation on the structures and electrochemical performances of the alloys was performed. The obtained results reveal that the as-cast and annealed alloys comprise two major phases, （La, Mg）2Ni7 phase with the hexagonal Ce2NiT-type structure and LaNi5 phase with the hexagonal CaCus-type structure, as well as a little residual LaNi3 phase. It is also found that the addition of Pr element observably affects the electrochemical hydrogen storage characteristics of the alloys, just as the discharge capacity and high rate discharge ability （HRD） first rise then fall with the growing of Pr content, and among all the alloys, the as-cast and annealed （x=0.3） alloys generate the largest discharge capacities of 360.8 and 386.5 mA.h/g, respectively. Additionally, the electrochemical cycle stability of all the alloys markedly grows with the increase of Pr content. The capacity retaining rate （S100） at the 100th charging and discharging cycle is enhanced from 64.98% to 77.55% for the as-cast alloy, and from 76.60% to 95.72% for the as-annealed alloy by rising Pr content from 0 to 0.4. Furthermore, the substitution of Pr for La results in first increase and then decrease in the hydrogen diffusion coefficient （D）, the limiting current density （IL） as well as the electrochemical impedance.
基金Project(2007AA11A104) supported by the High-tech Research and Development Program of ChinaProject(2009CB220100) supported by the National Basic Research Program of China
文摘A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys were characterized by XRD,EDS and SEM to investigate the effects of B and Fe substitution for Ni on material structure.The content of LaMg2Ni9 phase within La0.7Mg0.3Ni3 alloy reaches 37.9% and that of La0.7Mg0.3Ni2.9(FeB)0.1 alloys reduces to 23.58%.Among all samples,ground particles with different shapes correspond to different phases.The major substitution occurs in LaMg2Ni9 phase.Electrochemical tests indicate that substituted alloys have different electrochemical performance,which is affected by phase structures of alloy.The discharge capacity of La0.7Mg0.3Ni3 alloy reaches 337.3 mA·h/g,but La0.7Mg0.3Ni2.9(FeB)0.1 alloy gets better high rate discharge(HRD) performance at the discharge rate of 500 mA/g with a high HRD value of 73.19%.
基金supported by the National Natural Science Foundation of China(Grant No.51201089)the Priority Academic Program Development of Jiangsu Higher Education Institutions of China(PAPD)Specialized Research Fund for the Doctoral Program of Higher Education(Grant No.20133221110009)
文摘The Co-S/x wt.% AB5 （x=0, 10, 20, 30） composite materials were prepared by simply mixing Co-S material fabricated by hy- drothermal method and AB5 alloy. The structure and morphology of the composite materials were characterized by XRD and SEM, respectively. The electrochemical properties of the composite electrodes were studied by the galvanostatic charge, dis- charge test and electrochemical impedance spectroscopy. The results showed that the Co-S/20 wt.% AB5 composite electrode showed the highest discharge capacity and the best cycling stability. The existence of the AB5 alloy improved the electro- chemical activity of composite electrodes, reduced the electrochemical polarization resistances and promoted the electrochem- ical conversion reaction between Co and Co（OH）2. In order to improve the utilization rate of active materials, 0.0! mol/L Na2S203 was added into the electrolyte. The electrochemical properties of the composite electrode were significantly enhanced. After fifty cycles, the discharge capacity of the composite electrode increased from 407 to 481.7 mAh/g and the capacity reten- tion increased from 79.7% to 91.2%.
