To improve the electrochemical properties of rare-earth-Mg-Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the alloys were stud...To improve the electrochemical properties of rare-earth-Mg-Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the alloys were studied. Nonsubstituted Ml0.80Mg0.20（Ni2.90Co0.50-Mn0.30Al0.30）x （x=0.68, 0.70, 0.72, 0.74, 0.76） alloys and Cu-substituted Ml0.80Mg0.20（Ni2.90Co0.50-yCuyMn0.30Al0.30）0.70 （y=0, 0.10, 0.30, 0.50） alloys were prepared by induction melting. Phase structure analysis shows that the nonsubstituted alloys consist of a LaNi5 phase, a LaNi3 phase, and a minor La2Ni7 phase;in addition, in the case of Cu-substitution, the Nd2Ni7 phase appears and the LaNi3 phase vanishes. Ther-modynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with in-creasing stoichiometry and increasing Cu content. The maximum discharge capacity, kinetic properties, and cycling stability of the alloy electrodes all increase and then decrease with increasing stoichiometry or increasing Cu content. Furthermore, Cu substitution for Co ame-liorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.展开更多
The influences of Ca substitution for Ml and surface treatment on electrochemical performances of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 hydrogen storage alloy electrode were investigated. Ca substitution with x <0.2 ...The influences of Ca substitution for Ml and surface treatment on electrochemical performances of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 hydrogen storage alloy electrode were investigated. Ca substitution with x <0.2 for Ml could improve its discharge capacity, but Ca substitution with x >0.2 could decrease the capacity. It was also found that Ca substitution deteriorates the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode. In order to improve these properties of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 alloy electrode, the alloy was treated in 6 mol/L KOH+0.02 mol/L KBH 4 solution. The results showed that the surface treatment improves the electrochemical performances such as the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode. :The influences of Ca substitution for Ml and surface treatment on electrochemical performances of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 hydrogen storage alloy electrode were investigated. Ca substitution with x <0.2 for Ml could improve its discharge capacity, but Ca substitution with x >0.2 could decrease the capacity. It was also found that Ca substitution deteriorates the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode. In order to improve these properties of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 alloy electrode, the alloy was treated in 6 mol/L KOH+0.02 mol/L KBH 4 solution. The results showed that the surface treatment improves the electrochemical performances such as the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode.展开更多
The rapid development of electric vehicles demands the development of high performance nickel metal hydride battery that is able to endure high temperature. The discharge properties of Ti 0.7 Zr 0.5 V 0.2 Mn 1.8- x Ni...The rapid development of electric vehicles demands the development of high performance nickel metal hydride battery that is able to endure high temperature. The discharge properties of Ti 0.7 Zr 0.5 V 0.2 Mn 1.8- x Ni x ( x =0.4, 0.8, 1.1, 1.4, 1.7)hydrogen storage alloys was investigated and its phase composition was analyzed using X ray diffraction. The results show that the cycling life was improved as the content of nickel increases. When x =0.4, 0.8, 1.1 and 1.4, the main phase is MgZn 2 type C14 Laves phase and the second one is cubic TiNi phase. When x =1.7, the Laves phase structure disappears. EDAS analysis shows that the increase of nickel content is effective in suppressing the dissolution of vanadium component in alloys. [展开更多
In this paper, any two of the three anticorrosion agents, that is emulsifier (OP-10), soluble glass (Na2O·nSiO2) and glycerin (C3H8O3), were treated simultaneously on the surface of amorphous (a- ) MgNi + 5% Ml2M...In this paper, any two of the three anticorrosion agents, that is emulsifier (OP-10), soluble glass (Na2O·nSiO2) and glycerin (C3H8O3), were treated simultaneously on the surface of amorphous (a- ) MgNi + 5% Ml2Mg17(MI denotes the lanthanum-rich mish metal) electrode and the electrolyte. Effect of the synergistic anticorrosion treatment on charging/discharging cycle stability of the electrode was investigated. Contrasted with single treatment method, the cycling stability of the electrodes was further improved. The desirable synergistic anticorrosion method was that the electrode was treated by the soluble glass, and that OP-10 was added into the electrolyte. The cyclic voltammogram (CV) results of the electrode show clearly that the anticorrosion agent can change the electrochemical activity and mechanism of the electrode. The concentration of the anticorrosion agent in the electrolyte treated by the synergistic anticorrosion method was also investigated. The appropriate concentration of the anticorrosion agents in the electrolyte is 0.143% .展开更多
A series of multi-component M1-based hydrogen storage alloys witha cobalt atomic ratio of 0.40-0.75 were prepared. The electrochemicalproperties under different charge-discharge conditions and PCTcharaceristics measur...A series of multi-component M1-based hydrogen storage alloys witha cobalt atomic ratio of 0.40-0.75 were prepared. The electrochemicalproperties under different charge-discharge conditions and PCTcharaceristics measured by electrochemical method were investigated.The addition of other alloying elements for partial substitution ofCo low- ers the hydrogen equilibrium pressure and discharge capacity,but improves the cycling stability and makes the alloys keep nearlythe same rate discharge capability and high-temperature dischargecapability as those of the compared alloy. The reasons werediscussed.展开更多
The effect of the hot-charging treatment on the performance of AB(2) and AB(5) hydrogen storage alloy electrodes was investigated. The result showed that the treatment can markedly improve the voltage plateau ratio (V...The effect of the hot-charging treatment on the performance of AB(2) and AB(5) hydrogen storage alloy electrodes was investigated. The result showed that the treatment can markedly improve the voltage plateau ratio (VPR), the high rate discharge ability (HRDA), the diffusion coefficient of hydrogen DH and the discharge capacity of the AB2 hydrogen storage alloy electrode. The SEM analysis showed that the hot-charging treatment brings about a Ni-rich surface due to the dissolution of Zr oxides. It is also very helpful for the improvement of the kinetic properties of AB2 hydrogen storage alloy electrode because the microcracking of the surface results in fresh surface. This can be the basic modification treatment for NiMH battery used in electric vehicles (EVs) in the future. But for AB(5) type alloys, the treatment has the disadvantage of impairing the comprehensive electrochemical properties, because the surface of the alloy may be corroded during the treatment. The mechanism of the surface modification of the electrode is also proposed.展开更多
Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various tempera...Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various temperatures.Electrochemical reaction kinetic parameters were also studied with proper electrochemical techniques.The influence of the secondary corrosion reaction on the anodic linear polarization measurement was also analyzed by theoretical simulation.The results show that,proper ball-milling with nickel powders is beneficial to electrochemical performance.The theoretical simulation proves that,the existence of the side reaction can disturb the measurement of electrochemical reaction kinetic parameters.展开更多
The impedance diagram of hdrogen storage electrodes(AH electrodes )displayed twosemicircles.Thelow frequency one is affected by cycle number and composition of MH electrodes.
The microstructures and electrode properties of Cr or Co-doped V2.1 TiNi0.5 Hf0.05M 0.113 （M=Cr, Co） hydrogen storage alloys were investigated. It is found that all alloys consist of a main phase of V-based solid so...The microstructures and electrode properties of Cr or Co-doped V2.1 TiNi0.5 Hf0.05M 0.113 （M=Cr, Co） hydrogen storage alloys were investigated. It is found that all alloys consist of a main phase of V-based solid solution with b.c.c. structure and a secondary phase of C14-type Laves phase with a three-dimensional network structure. After the doping of Cr or Co into V 2.1TiNi 0.5Hf 0.05, the abundance and unit cell volume of the main phase decrease, and those of the secondary phase increase. The electrochemical measurements show that the discharge capacities of Cr-doped V2.1 TiNi0.5 Hf0.05Cr 0.113 alloy and Co-doped V2.1 TiNi0.5 Hf0.05Co 0.113 alloy are less than that of V2.1 TiNi0.5 Hf0.05 alloy, but their cycle stability and high-rate dischargeability are improved markedly. The results show that Cr or Co doping into V2.1 TiNi0.5 Hf0.05 alloy is significantly beneficial for the cycling stability.展开更多
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 micro...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.展开更多
The electrochemical properties of RE(NiCoMnTi) 5 hydrogen storage alloy with different composition of rare earth(RE=La 1-x-y-z Ce x Nd y Pr z ) components were systematically examined To display...The electrochemical properties of RE(NiCoMnTi) 5 hydrogen storage alloy with different composition of rare earth(RE=La 1-x-y-z Ce x Nd y Pr z ) components were systematically examined To display the effect of rare earth elements on the electrode properties, the comprehensive electrochemical property graphs including the discharge capacity, high dischargeability and cycling life of alloy electrode vs quasi ternary rare earth composition of multicomponent alloys were drawn by first dividing the component elements into two groups with fixed ratios between the two groups and then using a computer program for engineering graphics By the optimizaiton of the La∶Ce∶Nd∶Pr ratio, the alloy RE(NiCoMnTi) 5 shows a maximum capacity of 290 mAh/g and good cycling stability The higher capacity was due to the larger unit cell volume of the alloy with RE=La 0 4 Ce 0 1 Nd 0 3 Pr 0 2 , as determined by X ray diffraction analysis展开更多
On the basis of typical high Co MI(Lanthanum rich mischmetal) based hydrogen storage alloy, a series oflow Co or Co free alloys have been prepared by means of partial or full replacement of Co by a combination of othe...On the basis of typical high Co MI(Lanthanum rich mischmetal) based hydrogen storage alloy, a series oflow Co or Co free alloys have been prepared by means of partial or full replacement of Co by a combination of other elements. The microstructures, p c T (pressure concentration temperature) characteristics and electrochemical propertiesunder different charge discharge conditions of the alloys have been investigated. Compared with the high Co alloy, thelow Co or Co free alloys have the lower hydrogen equilibrium pressure and discharge capacity, but have the nearly samehigh rate and high temperature discharge capability, and better charge discharge cycling stability. The reason is revealedby SEM, XPS and XRD results. \[展开更多
A hydrogen storage electrode alloy La_ 0.7Mg_ 0.3Ni_ 2.98Co_ 0.52 was obtained by electromagnetism inductive melting of alloys such as La, Mg, Ni and Co. XRD analyses indicate that the microstructure of the prepared a...A hydrogen storage electrode alloy La_ 0.7Mg_ 0.3Ni_ 2.98Co_ 0.52 was obtained by electromagnetism inductive melting of alloys such as La, Mg, Ni and Co. XRD analyses indicate that the microstructure of the prepared alloy was composed of LaNi_5 phase as matrix and another unknown phase as secondary phase. In this experiment, the highest discharge capacity of alloy is 378 mAh·g -1 at 293 K, which is 20% higher than the discharge capacity of LaNi_5-type alloys. The alloy was activated after two cycles and the discharge potential is high and stable, and more than 90% of the discharge time is in a voltage higher than 1.2 V. However, the cycle stability is poor as practical application, to improve the cycle life of the alloy becomes the key factor. Moreover, the loose structure of the alloy is maybe one reason that makes the cycle stability capacity of the alloy decrease by SEM.展开更多
Hydrogen diffusion coefficients in MlNi 3.75 Co 0.65 Mn 0.4 Al 0.2 alloy electrode as a function of state of charge (SOC) or temperature were determined by chronoamperometry. It is found that hydrogen diffusion coeffi...Hydrogen diffusion coefficients in MlNi 3.75 Co 0.65 Mn 0.4 Al 0.2 alloy electrode as a function of state of charge (SOC) or temperature were determined by chronoamperometry. It is found that hydrogen diffusion coefficient decreases with the increase of SOC or the decrease of temperature. The activation energy for hydrogen diffusion in the alloy electrode with 50%SOC is evaluated to be 19.9?kJ/mol.展开更多
The crystallographic structure, microstructure, composition homogeneity and electrode charge-discharge cycling stability were investigated of the as-cast and annealed La-rich mischmetal (designating Ml)-based hydrogen...The crystallographic structure, microstructure, composition homogeneity and electrode charge-discharge cycling stability were investigated of the as-cast and annealed La-rich mischmetal (designating Ml)-based hydrogen storage alloy with a composition of MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3). X-ray diffraction analysis shows that the MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) alloy is composed of the dominant phase with a CaCu_5-type hexagonal structure and small amounts of the second phase with a La_2Ni_7-type structure. The annealing heat treatment conducted at 1273 K for 10 h results in decrease of the crystal lattice strain and composition segregation, disappearance of the dendrite structure and growth of the crystal grain of the MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) alloy. The annealing causes the cycle life to be increased by about 30% over the as-cast alloy electrode. The cycling stability of the alloy electrode is improved significantly upon annealing. The cause of the improvement in the cycling stability was discussed based on the alloy composition distribution and microstructure changes due to annealing.展开更多
The electrochemical process of Ti-Ni alloy electrode was studied by using cyclic voltammetry. The hydrogen-absorbing electrode could be approximately regarded as a reversible hydrogen elecrede. The con- trolling steps...The electrochemical process of Ti-Ni alloy electrode was studied by using cyclic voltammetry. The hydrogen-absorbing electrode could be approximately regarded as a reversible hydrogen elecrede. The con- trolling steps of the discharging process varying with the anodic overpotentials were investigated and the effect ofelecrode constituent modification or Zr adulteation on the electrochemical behavior was also studied.展开更多
Nano meter sized WC powder (1～20 nm) was synthesized by mechanochemical explosion synthesis. The catalytic property of WC powder was discovered to decompose the molecular water and chemical adsorb H atoms in KOH solu...Nano meter sized WC powder (1～20 nm) was synthesized by mechanochemical explosion synthesis. The catalytic property of WC powder was discovered to decompose the molecular water and chemical adsorb H atoms in KOH solution, and accelerate the combination reaction of hydrogen during the cathodic polarization, thus a negative effect on the activation was found because of easy H 2 emission. Electrochemical impedance spectroscopy (EIS) showed that the adsorbed hydrogen atoms on the surface of WC are first electrochemically oxidized due to their lower chemical bonding, and that the low conductivity of WC powder also increases the internal resistance of electrodes.展开更多
The effect of La alloying on the crystalline characteristics, electrochemical capacity and activity of AB2 type Zr-Cr-Ni hydride electrodes was investigated. It was found that La alloying was able to shorten the activ...The effect of La alloying on the crystalline characteristics, electrochemical capacity and activity of AB2 type Zr-Cr-Ni hydride electrodes was investigated. It was found that La alloying was able to shorten the activating process from 15 cycles of La-free alloy to 2 cycles, and that the main phase shifts from C14 to C15 by XRD analysis. It may be attributed to the modification of surface chemical states and change in internal microstructures. However, the cycling stability was also found to degrade severely for La-containing hydride electrode because of the collapse of its distorted lattice.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21303157 and 21106123)the Natural Science Foundation of Hebei Province,China(No.B2012203104)+1 种基金the China Postdoctoral Science Foundation Project(2013M541201)the Research Fund for the Doctoral Program of Higher Education of China(20131333120008)
文摘To improve the electrochemical properties of rare-earth-Mg-Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the alloys were studied. Nonsubstituted Ml0.80Mg0.20（Ni2.90Co0.50-Mn0.30Al0.30）x （x=0.68, 0.70, 0.72, 0.74, 0.76） alloys and Cu-substituted Ml0.80Mg0.20（Ni2.90Co0.50-yCuyMn0.30Al0.30）0.70 （y=0, 0.10, 0.30, 0.50） alloys were prepared by induction melting. Phase structure analysis shows that the nonsubstituted alloys consist of a LaNi5 phase, a LaNi3 phase, and a minor La2Ni7 phase;in addition, in the case of Cu-substitution, the Nd2Ni7 phase appears and the LaNi3 phase vanishes. Ther-modynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with in-creasing stoichiometry and increasing Cu content. The maximum discharge capacity, kinetic properties, and cycling stability of the alloy electrodes all increase and then decrease with increasing stoichiometry or increasing Cu content. Furthermore, Cu substitution for Co ame-liorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.
文摘The influences of Ca substitution for Ml and surface treatment on electrochemical performances of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 hydrogen storage alloy electrode were investigated. Ca substitution with x <0.2 for Ml could improve its discharge capacity, but Ca substitution with x >0.2 could decrease the capacity. It was also found that Ca substitution deteriorates the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode. In order to improve these properties of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 alloy electrode, the alloy was treated in 6 mol/L KOH+0.02 mol/L KBH 4 solution. The results showed that the surface treatment improves the electrochemical performances such as the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode. :The influences of Ca substitution for Ml and surface treatment on electrochemical performances of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 hydrogen storage alloy electrode were investigated. Ca substitution with x <0.2 for Ml could improve its discharge capacity, but Ca substitution with x >0.2 could decrease the capacity. It was also found that Ca substitution deteriorates the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode. In order to improve these properties of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 alloy electrode, the alloy was treated in 6 mol/L KOH+0.02 mol/L KBH 4 solution. The results showed that the surface treatment improves the electrochemical performances such as the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode.
文摘The rapid development of electric vehicles demands the development of high performance nickel metal hydride battery that is able to endure high temperature. The discharge properties of Ti 0.7 Zr 0.5 V 0.2 Mn 1.8- x Ni x ( x =0.4, 0.8, 1.1, 1.4, 1.7)hydrogen storage alloys was investigated and its phase composition was analyzed using X ray diffraction. The results show that the cycling life was improved as the content of nickel increases. When x =0.4, 0.8, 1.1 and 1.4, the main phase is MgZn 2 type C14 Laves phase and the second one is cubic TiNi phase. When x =1.7, the Laves phase structure disappears. EDAS analysis shows that the increase of nickel content is effective in suppressing the dissolution of vanadium component in alloys. [
基金Project supported by the National Natural Science Foundation of China (20363001) the Project in Specific Technological R & D Fund Program for Research Institutes from Ministry of Science and Technology of the PRC (2004EG113030)the Key Project in International Science and Technology Cooperation from Ministry of Science and Technology of the PRC (2005DFA50250)
文摘In this paper, any two of the three anticorrosion agents, that is emulsifier (OP-10), soluble glass (Na2O·nSiO2) and glycerin (C3H8O3), were treated simultaneously on the surface of amorphous (a- ) MgNi + 5% Ml2Mg17(MI denotes the lanthanum-rich mish metal) electrode and the electrolyte. Effect of the synergistic anticorrosion treatment on charging/discharging cycle stability of the electrode was investigated. Contrasted with single treatment method, the cycling stability of the electrodes was further improved. The desirable synergistic anticorrosion method was that the electrode was treated by the soluble glass, and that OP-10 was added into the electrolyte. The cyclic voltammogram (CV) results of the electrode show clearly that the anticorrosion agent can change the electrochemical activity and mechanism of the electrode. The concentration of the anticorrosion agent in the electrolyte treated by the synergistic anticorrosion method was also investigated. The appropriate concentration of the anticorrosion agents in the electrolyte is 0.143% .
文摘A series of multi-component M1-based hydrogen storage alloys witha cobalt atomic ratio of 0.40-0.75 were prepared. The electrochemicalproperties under different charge-discharge conditions and PCTcharaceristics measured by electrochemical method were investigated.The addition of other alloying elements for partial substitution ofCo low- ers the hydrogen equilibrium pressure and discharge capacity,but improves the cycling stability and makes the alloys keep nearlythe same rate discharge capability and high-temperature dischargecapability as those of the compared alloy. The reasons werediscussed.
文摘The effect of the hot-charging treatment on the performance of AB(2) and AB(5) hydrogen storage alloy electrodes was investigated. The result showed that the treatment can markedly improve the voltage plateau ratio (VPR), the high rate discharge ability (HRDA), the diffusion coefficient of hydrogen DH and the discharge capacity of the AB2 hydrogen storage alloy electrode. The SEM analysis showed that the hot-charging treatment brings about a Ni-rich surface due to the dissolution of Zr oxides. It is also very helpful for the improvement of the kinetic properties of AB2 hydrogen storage alloy electrode because the microcracking of the surface results in fresh surface. This can be the basic modification treatment for NiMH battery used in electric vehicles (EVs) in the future. But for AB(5) type alloys, the treatment has the disadvantage of impairing the comprehensive electrochemical properties, because the surface of the alloy may be corroded during the treatment. The mechanism of the surface modification of the electrode is also proposed.
文摘Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various temperatures.Electrochemical reaction kinetic parameters were also studied with proper electrochemical techniques.The influence of the secondary corrosion reaction on the anodic linear polarization measurement was also analyzed by theoretical simulation.The results show that,proper ball-milling with nickel powders is beneficial to electrochemical performance.The theoretical simulation proves that,the existence of the side reaction can disturb the measurement of electrochemical reaction kinetic parameters.
文摘The impedance diagram of hdrogen storage electrodes(AH electrodes )displayed twosemicircles.Thelow frequency one is affected by cycle number and composition of MH electrodes.
文摘The microstructures and electrode properties of Cr or Co-doped V2.1 TiNi0.5 Hf0.05M 0.113 （M=Cr, Co） hydrogen storage alloys were investigated. It is found that all alloys consist of a main phase of V-based solid solution with b.c.c. structure and a secondary phase of C14-type Laves phase with a three-dimensional network structure. After the doping of Cr or Co into V 2.1TiNi 0.5Hf 0.05, the abundance and unit cell volume of the main phase decrease, and those of the secondary phase increase. The electrochemical measurements show that the discharge capacities of Cr-doped V2.1 TiNi0.5 Hf0.05Cr 0.113 alloy and Co-doped V2.1 TiNi0.5 Hf0.05Co 0.113 alloy are less than that of V2.1 TiNi0.5 Hf0.05 alloy, but their cycle stability and high-rate dischargeability are improved markedly. The results show that Cr or Co doping into V2.1 TiNi0.5 Hf0.05 alloy is significantly beneficial for the cycling stability.
基金Project(50171021) supported by the National Natural Science Foundation of China
文摘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.
文摘The electrochemical properties of RE(NiCoMnTi) 5 hydrogen storage alloy with different composition of rare earth(RE=La 1-x-y-z Ce x Nd y Pr z ) components were systematically examined To display the effect of rare earth elements on the electrode properties, the comprehensive electrochemical property graphs including the discharge capacity, high dischargeability and cycling life of alloy electrode vs quasi ternary rare earth composition of multicomponent alloys were drawn by first dividing the component elements into two groups with fixed ratios between the two groups and then using a computer program for engineering graphics By the optimizaiton of the La∶Ce∶Nd∶Pr ratio, the alloy RE(NiCoMnTi) 5 shows a maximum capacity of 290 mAh/g and good cycling stability The higher capacity was due to the larger unit cell volume of the alloy with RE=La 0 4 Ce 0 1 Nd 0 3 Pr 0 2 , as determined by X ray diffraction analysis
文摘On the basis of typical high Co MI(Lanthanum rich mischmetal) based hydrogen storage alloy, a series oflow Co or Co free alloys have been prepared by means of partial or full replacement of Co by a combination of other elements. The microstructures, p c T (pressure concentration temperature) characteristics and electrochemical propertiesunder different charge discharge conditions of the alloys have been investigated. Compared with the high Co alloy, thelow Co or Co free alloys have the lower hydrogen equilibrium pressure and discharge capacity, but have the nearly samehigh rate and high temperature discharge capability, and better charge discharge cycling stability. The reason is revealedby SEM, XPS and XRD results. \[
文摘A hydrogen storage electrode alloy La_ 0.7Mg_ 0.3Ni_ 2.98Co_ 0.52 was obtained by electromagnetism inductive melting of alloys such as La, Mg, Ni and Co. XRD analyses indicate that the microstructure of the prepared alloy was composed of LaNi_5 phase as matrix and another unknown phase as secondary phase. In this experiment, the highest discharge capacity of alloy is 378 mAh·g -1 at 293 K, which is 20% higher than the discharge capacity of LaNi_5-type alloys. The alloy was activated after two cycles and the discharge potential is high and stable, and more than 90% of the discharge time is in a voltage higher than 1.2 V. However, the cycle stability is poor as practical application, to improve the cycle life of the alloy becomes the key factor. Moreover, the loose structure of the alloy is maybe one reason that makes the cycle stability capacity of the alloy decrease by SEM.
文摘Hydrogen diffusion coefficients in MlNi 3.75 Co 0.65 Mn 0.4 Al 0.2 alloy electrode as a function of state of charge (SOC) or temperature were determined by chronoamperometry. It is found that hydrogen diffusion coefficient decreases with the increase of SOC or the decrease of temperature. The activation energy for hydrogen diffusion in the alloy electrode with 50%SOC is evaluated to be 19.9?kJ/mol.
文摘The crystallographic structure, microstructure, composition homogeneity and electrode charge-discharge cycling stability were investigated of the as-cast and annealed La-rich mischmetal (designating Ml)-based hydrogen storage alloy with a composition of MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3). X-ray diffraction analysis shows that the MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) alloy is composed of the dominant phase with a CaCu_5-type hexagonal structure and small amounts of the second phase with a La_2Ni_7-type structure. The annealing heat treatment conducted at 1273 K for 10 h results in decrease of the crystal lattice strain and composition segregation, disappearance of the dendrite structure and growth of the crystal grain of the MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) alloy. The annealing causes the cycle life to be increased by about 30% over the as-cast alloy electrode. The cycling stability of the alloy electrode is improved significantly upon annealing. The cause of the improvement in the cycling stability was discussed based on the alloy composition distribution and microstructure changes due to annealing.
文摘The electrochemical process of Ti-Ni alloy electrode was studied by using cyclic voltammetry. The hydrogen-absorbing electrode could be approximately regarded as a reversible hydrogen elecrede. The con- trolling steps of the discharging process varying with the anodic overpotentials were investigated and the effect ofelecrode constituent modification or Zr adulteation on the electrochemical behavior was also studied.
文摘Nano meter sized WC powder (1～20 nm) was synthesized by mechanochemical explosion synthesis. The catalytic property of WC powder was discovered to decompose the molecular water and chemical adsorb H atoms in KOH solution, and accelerate the combination reaction of hydrogen during the cathodic polarization, thus a negative effect on the activation was found because of easy H 2 emission. Electrochemical impedance spectroscopy (EIS) showed that the adsorbed hydrogen atoms on the surface of WC are first electrochemically oxidized due to their lower chemical bonding, and that the low conductivity of WC powder also increases the internal resistance of electrodes.
文摘The effect of La alloying on the crystalline characteristics, electrochemical capacity and activity of AB2 type Zr-Cr-Ni hydride electrodes was investigated. It was found that La alloying was able to shorten the activating process from 15 cycles of La-free alloy to 2 cycles, and that the main phase shifts from C14 to C15 by XRD analysis. It may be attributed to the modification of surface chemical states and change in internal microstructures. However, the cycling stability was also found to degrade severely for La-containing hydride electrode because of the collapse of its distorted lattice.
