Rare earth-Mg-Ni-based alloys with superlattice structures are new generation negative electrode materials for the nickel metal hydride batteries.Among them,the novel AB_(4)-type superlattice structure alloy is suppos...Rare earth-Mg-Ni-based alloys with superlattice structures are new generation negative electrode materials for the nickel metal hydride batteries.Among them,the novel AB_(4)-type superlattice structure alloy is supposed to have superior cycling stability and rate capability.Yet its preparation is hindered by the crucial requirement of temperature and the special composition which is close to the other superlattice structure.Here,we prepare rare earth-Mg-Ni-based alloy and study the phase transformation of alloys to make clear the formation of AB_(4)-type phase.It is found Pr_(5)Co_(19)-type phase is converted from Ce_(5)Co_(19)-type phase and shows good stability at higher temperature compared to the Ce_(5)Co_(19)-type phase in the range of 930-970℃.Afterwards,with further 5℃increasing,AB_(4)-type superlattice structure forms at a temperature of 975℃by consuming Pr_(5)Co_(19)-type phase.In contrast with A_(5)B_(19)-type alloy,AB_(4)-type alloy has superior rate capability owing to the dominant advantages of charge transfer and hydrogen diffusion.Besides,AB_(4)-type alloy shows long lifespan whose capacity retention rates are 89.2%at the 100;cycle and 82.8%at the 200;cycle,respectively.AB_(4)-type alloy delivers 1.53 wt.%hydrogen storage capacity at room temperature and exhibits higher plateau pressure than Pr_(5)Co_(19)-type alloy.The work provides novel AB_(4)-type alloy with preferable electrochemical performance as negative electrode material to inspire the development of nickel metal hydride batteries.展开更多
The Acidithiobacillus ferrooxidans （At. f） and Acidithiobacillus thiooxidans （At. t ） were used in bio-dissolution experiments of heavy metals in spent MH/Ni batteries. The influences of the initial pH value, the ...The Acidithiobacillus ferrooxidans （At. f） and Acidithiobacillus thiooxidans （At. t ） were used in bio-dissolution experiments of heavy metals in spent MH/Ni batteries. The influences of the initial pH value, the concentration of electrode materials, the temperature and substrate concentration on the leaching rate of heavy metal Ni, Co have been investigated. The obtained results indicate that the efficiency of nickel extrac- tion and cobalt extraction is dependent on all of the mentioned factors. Especially, the initial pH value and the temperature have more effect than other factors for these microorganisms. In addition, the results show that the optimal leaching rate of Ni and Co in the spent MH/Ni batteries reaches to 95.7 % and 72.4 % respectively after 20 days under the conditions of the initial pH value 1.0, concentration of electrode materials 1.0 %, temperature 30°C and substrate（sulfur） concentration 4.0 g＇L^-1.展开更多
The effects of overcharge on electrochemical performance of AA size sealed-type nickel/metal hydride（Ni/MH） batteries and its degradation mechanism were investigated. The results indicated that the relationship betw...The effects of overcharge on electrochemical performance of AA size sealed-type nickel/metal hydride（Ni/MH） batteries and its degradation mechanism were investigated. The results indicated that the relationship between the effects of different overcharge currents on the increasing velocity of inner pressure and the degradation velocity of cycle life and discharge voltage remains in almost direct proportion. After overcharge cycles, the positive electrode materials remain the original structure, but there occur some breaks because of the irreversible expand of crystal lattice. And the negative electrode alloy particles have inconspicuous pulverization, but are covered with lots of corrosive products and its main component is rare earth hydroxide or oxide. These are all the main reasons leading to the degradation behavior of the discharge capacity and cycle life of Ni/MH batteries.展开更多
A series of positive electrodes for Ni/MH battery were fabricated by addition of CoO.The morphology and microstructure of the electrodes were examined by SEM and EDS, and electrochemical behavior was investigated in t...A series of positive electrodes for Ni/MH battery were fabricated by addition of CoO.The morphology and microstructure of the electrodes were examined by SEM and EDS, and electrochemical behavior was investigated in three-compartment appliances at room temperature.The electrochemical performance of the positive electrodes with CoO was improved. Under the same charge-discharge cycle, the electrodes with CoO showed higher specific capacity, lower charge mean voltage and higher discharge mean voltage. But ...展开更多
Negative electrodes of the nickel-metal hydride battery were made from hydrogen storage alloy Mm0.9Ti0.1Ni3.9Mn0.4Co0.4Al0.3 modified by coating with nickei and mixing with cobalt powder. When the 10wt% cobalt powder ...Negative electrodes of the nickel-metal hydride battery were made from hydrogen storage alloy Mm0.9Ti0.1Ni3.9Mn0.4Co0.4Al0.3 modified by coating with nickei and mixing with cobalt powder. When the 10wt% cobalt powder was mixed with this alloy, the discharge capacity increased from 262 mAh/g to 300 mAh/g at 300K. When the alloy was coated with 11wt% nickel and mixed with 10wt% cobalt powder, the discharge capacity decay for a sealed cell (AA size, 1 Ah) was only about 4% after 200 cycles.展开更多
In this work,we synthesized LaFeO_3–xwt%Ni(x=0,5,10,15)composites via a solid-state reaction method by adding Ni to the reactants,La_2O_3 and Fe_2O_3.Field-emission scanning electron microscopy(FE-SEM)and energy-disp...In this work,we synthesized LaFeO_3–xwt%Ni(x=0,5,10,15)composites via a solid-state reaction method by adding Ni to the reactants,La_2O_3 and Fe_2O_3.Field-emission scanning electron microscopy(FE-SEM)and energy-dispersive X-ray spectroscopy(EDS)results revealed that Ni powders evenly dispersed among the LaFeO_3 particles and apparently reduced their aggregation,which imparted the composites with a loose structure.Moreover,the Ni formed a conductive network,thus improving the conductivity of the composites.The maximum discharge capacity of the LaFeO_3 electrodes remarkably increased from 266.8 mAh·g^(–1)(x=0)to 339.7 mAh·g^(–1)(x=10).In particular,the high-rate dischargeability of the LaFeO_3–10wt%Ni electrode at a discharge current density of 1500 mA·g^(-1) reached 54.6%,which was approximately 1.5 times higher than that of the pure LaFeO_3.Such a Ni-modified loose structure not only increased the charge transfer rate on the surface of the LaFeO_3 particles but also enhanced the hydrogen diffusion rate in the bulk LaFeO_3.展开更多
The nonstoichiometric La-rich mischmetal (designated by MI)-based hydrogen storage alloy with a composition of MI(Ni0.64Co0.2Mn0.12Al0.04)(4.76) was prepared by arc melting and annealed at 1173 K for 10 h to investiga...The nonstoichiometric La-rich mischmetal (designated by MI)-based hydrogen storage alloy with a composition of MI(Ni0.64Co0.2Mn0.12Al0.04)(4.76) was prepared by arc melting and annealed at 1173 K for 10 h to investigate the effect of annealing treatment on the microstructure and electrochemical characteristics of the alloy. X-ray diffraction analysis showed that annealing can cause a release of the crystal lattice strain and an increase in amounts of the La2Ni7-type second phase in MI(Ni0.64Co0.20Mn0.12Al0.04)(4.76) alloy. Scanning electron microscopy and electron probe microanalysis examinations indicated that annealing leads to disappearance of the dendrite structure in the as-cast alloy, growth of crystal grain, and decrease of composition segregation. The annealing at 1173 K for 10 h flattened and extended the potential plateau and increased the maximum discharge capacity to 328 mA center dot h/g from 310 mA center dot h/g and the cycling life. The mechanism of the improvement in electrochemical characteristics was discussed based on the alloy microstructure change induced by annealing.展开更多
It is discovered that the consistency of negative electrode is one of the main influences on battery performance, since the main raw material in negative electrode is metal hydride powder, ingredients, particle distri...It is discovered that the consistency of negative electrode is one of the main influences on battery performance, since the main raw material in negative electrode is metal hydride powder, ingredients, particle distribution and density of the powder could influence the pasting consistency in some aspects.With the study of MH powder characteristics, through the modification of the coating die, the consistency of negative electrode is improved efficiently.展开更多
The electrochemical characteristics and crystal structure of metal hydride electrode of AB_(3.5)-type alloy was studied. The electrochemical properties of the metal hydride electrode were investigated at room temperat...The electrochemical characteristics and crystal structure of metal hydride electrode of AB_(3.5)-type alloy was studied. The electrochemical properties of the metal hydride electrode were investigated at room temperature and -30 ℃. The partial substitution of Ni by Al element causes an expansion of the lattice cell and increases the specific capacity and rate discharge ability of the alloy.展开更多
The Co(Ⅲ)-coated spherical nickel hydroxide powder is optimum as positive electrode of high power Ni-MH battery because of its excellent property. But the performances at high temperature(above 50 ℃) is still not sa...The Co(Ⅲ)-coated spherical nickel hydroxide powder is optimum as positive electrode of high power Ni-MH battery because of its excellent property. But the performances at high temperature(above 50 ℃) is still not satisfied. In the present paper,the effect of element erbium,used as additive by different methods to prepare positive electrode,on the high temperature performances of the Ni-MH batteries is studied. It is found that the charge acceptance ability of the spherical Ni(OH)2 electrode with element erbium as additive is improved. The discharge capacities of Ni(OH)2 coated with 1%(atomic fraction) Er(OH)3 and mechanically added with 1%(atomic fraction) Er2O3 at 1C are 12.6% and 11.7%,respectively,higher than those of the samples without erbium at 70 ℃.展开更多
We reported the effects of annealing temperatures on microstructure and electrochemical properties of perovskite-type oxide LaFeO3 prepared by stearic acid combustion method. X-Ray diffraction（XRD） patterns show tha...We reported the effects of annealing temperatures on microstructure and electrochemical properties of perovskite-type oxide LaFeO3 prepared by stearic acid combustion method. X-Ray diffraction（XRD） patterns show that the annealed LaFeO3 powder has orthorhombic structure. Scanning electron microscopy（SEM） and transmission electron microscopy（TEM） images show the presence of homogeneously dispersed, less aggregated, and small crystals（30--40 nm） at annealing temperatures of 500 and 600 ℃. However, as the annealing temperature was increased to 700 and 800 ℃, the crystals began to combine with each other and grew into further larger crystals（90--100 nm）. The electrochemical performance of the annealed oxides was measured at 60 ℃ using chronopotentiometry, potentiodynamic polarization, and cyclic voltammetry. As the annealing temperature increased, the discharge capacity and anti-corrosion ability of the oxide electrode first increased and then decreased, reaching the optimum values at 600 ℃, with a maximum discharge capacity of 563 mA-h/g. The better electrochemical performance of LaFeO3 annealed at 600℃ could be ascribed to their smaller and more homogeneous crysals.展开更多
基金financially supported by the Natural Science Foundation of Hebei Province(Nos.E2019203414,E2020203081 and E2019203161)the National Natural Science Foundation of China(Nos.51701175 and 51971197)+1 种基金the Innovation Fund for the Graduate Students of Hebei Province(No.CXZZBS2020062)the Doctoral Fund of Yanshan University(No.BL19031)
文摘Rare earth-Mg-Ni-based alloys with superlattice structures are new generation negative electrode materials for the nickel metal hydride batteries.Among them,the novel AB_(4)-type superlattice structure alloy is supposed to have superior cycling stability and rate capability.Yet its preparation is hindered by the crucial requirement of temperature and the special composition which is close to the other superlattice structure.Here,we prepare rare earth-Mg-Ni-based alloy and study the phase transformation of alloys to make clear the formation of AB_(4)-type phase.It is found Pr_(5)Co_(19)-type phase is converted from Ce_(5)Co_(19)-type phase and shows good stability at higher temperature compared to the Ce_(5)Co_(19)-type phase in the range of 930-970℃.Afterwards,with further 5℃increasing,AB_(4)-type superlattice structure forms at a temperature of 975℃by consuming Pr_(5)Co_(19)-type phase.In contrast with A_(5)B_(19)-type alloy,AB_(4)-type alloy has superior rate capability owing to the dominant advantages of charge transfer and hydrogen diffusion.Besides,AB_(4)-type alloy shows long lifespan whose capacity retention rates are 89.2%at the 100;cycle and 82.8%at the 200;cycle,respectively.AB_(4)-type alloy delivers 1.53 wt.%hydrogen storage capacity at room temperature and exhibits higher plateau pressure than Pr_(5)Co_(19)-type alloy.The work provides novel AB_(4)-type alloy with preferable electrochemical performance as negative electrode material to inspire the development of nickel metal hydride batteries.
基金Supported by the Natural Science Foundation of Department of Education （05Z008） and the Science and Technology Projects of Guangdong Province （2007B030101007）.
文摘有高特定的体积能力的圆柱的镍金属氢化物(Ni-MH ) 电池被使用 oxyhydroxide Ni 准备(哦) 2 并且 AB5 类型氢存储合金并且调整积极、否定的电极的设计参数。oxyhydroxide Ni (哦) 2 被氧化综合有化学方法的球形的 -Ni(OH)2。X 光检查衍射(XRD ) 模式和 Fourier 转变红外线(英尺红外) 系列显示 -NiOOH 在 oxyhydroxide Ni 上被形成(哦) 2 粉末，和一些 H2O 分子被插入到他们的晶体格子间距。当时，电池能力不能被改进 oxyhydroxide Ni (哦) 2 样品直接被用作积极活跃材料。然而，基于传导力和 oxyhydroxide Ni 的剩余能力(哦) 2 搽粉，与 2560 妈一起的 AA 尺寸 Ni-MH 电池？
基金Sponsored by the National Basic Research Program of China (2002CB211800)
文摘The Acidithiobacillus ferrooxidans （At. f） and Acidithiobacillus thiooxidans （At. t ） were used in bio-dissolution experiments of heavy metals in spent MH/Ni batteries. The influences of the initial pH value, the concentration of electrode materials, the temperature and substrate concentration on the leaching rate of heavy metal Ni, Co have been investigated. The obtained results indicate that the efficiency of nickel extrac- tion and cobalt extraction is dependent on all of the mentioned factors. Especially, the initial pH value and the temperature have more effect than other factors for these microorganisms. In addition, the results show that the optimal leaching rate of Ni and Co in the spent MH/Ni batteries reaches to 95.7 % and 72.4 % respectively after 20 days under the conditions of the initial pH value 1.0, concentration of electrode materials 1.0 %, temperature 30°C and substrate（sulfur） concentration 4.0 g＇L^-1.
文摘The effects of overcharge on electrochemical performance of AA size sealed-type nickel/metal hydride（Ni/MH） batteries and its degradation mechanism were investigated. The results indicated that the relationship between the effects of different overcharge currents on the increasing velocity of inner pressure and the degradation velocity of cycle life and discharge voltage remains in almost direct proportion. After overcharge cycles, the positive electrode materials remain the original structure, but there occur some breaks because of the irreversible expand of crystal lattice. And the negative electrode alloy particles have inconspicuous pulverization, but are covered with lots of corrosive products and its main component is rare earth hydroxide or oxide. These are all the main reasons leading to the degradation behavior of the discharge capacity and cycle life of Ni/MH batteries.
基金supported by the National High Technology Development Program of China (No. 2003AA302420)the National Major Basic Research Project (No. GT20000264-06) of MOST, China
文摘A series of positive electrodes for Ni/MH battery were fabricated by addition of CoO.The morphology and microstructure of the electrodes were examined by SEM and EDS, and electrochemical behavior was investigated in three-compartment appliances at room temperature.The electrochemical performance of the positive electrodes with CoO was improved. Under the same charge-discharge cycle, the electrodes with CoO showed higher specific capacity, lower charge mean voltage and higher discharge mean voltage. But ...
文摘Negative electrodes of the nickel-metal hydride battery were made from hydrogen storage alloy Mm0.9Ti0.1Ni3.9Mn0.4Co0.4Al0.3 modified by coating with nickei and mixing with cobalt powder. When the 10wt% cobalt powder was mixed with this alloy, the discharge capacity increased from 262 mAh/g to 300 mAh/g at 300K. When the alloy was coated with 11wt% nickel and mixed with 10wt% cobalt powder, the discharge capacity decay for a sealed cell (AA size, 1 Ah) was only about 4% after 200 cycles.
基金financially supported by the National Natural Science Foundation of China(Nos.51771164,51571173,and 51701175)the National Postdoctoral Program for Innovative Talents of China(No.BX201700204)the Innovation Fund for the Graduate Students of Hebei Province(No.CXZZBS2017057)
文摘In this work,we synthesized LaFeO_3–xwt%Ni(x=0,5,10,15)composites via a solid-state reaction method by adding Ni to the reactants,La_2O_3 and Fe_2O_3.Field-emission scanning electron microscopy(FE-SEM)and energy-dispersive X-ray spectroscopy(EDS)results revealed that Ni powders evenly dispersed among the LaFeO_3 particles and apparently reduced their aggregation,which imparted the composites with a loose structure.Moreover,the Ni formed a conductive network,thus improving the conductivity of the composites.The maximum discharge capacity of the LaFeO_3 electrodes remarkably increased from 266.8 mAh·g^(–1)(x=0)to 339.7 mAh·g^(–1)(x=10).In particular,the high-rate dischargeability of the LaFeO_3–10wt%Ni electrode at a discharge current density of 1500 mA·g^(-1) reached 54.6%,which was approximately 1.5 times higher than that of the pure LaFeO_3.Such a Ni-modified loose structure not only increased the charge transfer rate on the surface of the LaFeO_3 particles but also enhanced the hydrogen diffusion rate in the bulk LaFeO_3.
文摘The nonstoichiometric La-rich mischmetal (designated by MI)-based hydrogen storage alloy with a composition of MI(Ni0.64Co0.2Mn0.12Al0.04)(4.76) was prepared by arc melting and annealed at 1173 K for 10 h to investigate the effect of annealing treatment on the microstructure and electrochemical characteristics of the alloy. X-ray diffraction analysis showed that annealing can cause a release of the crystal lattice strain and an increase in amounts of the La2Ni7-type second phase in MI(Ni0.64Co0.20Mn0.12Al0.04)(4.76) alloy. Scanning electron microscopy and electron probe microanalysis examinations indicated that annealing leads to disappearance of the dendrite structure in the as-cast alloy, growth of crystal grain, and decrease of composition segregation. The annealing at 1173 K for 10 h flattened and extended the potential plateau and increased the maximum discharge capacity to 328 mA center dot h/g from 310 mA center dot h/g and the cycling life. The mechanism of the improvement in electrochemical characteristics was discussed based on the alloy microstructure change induced by annealing.
文摘It is discovered that the consistency of negative electrode is one of the main influences on battery performance, since the main raw material in negative electrode is metal hydride powder, ingredients, particle distribution and density of the powder could influence the pasting consistency in some aspects.With the study of MH powder characteristics, through the modification of the coating die, the consistency of negative electrode is improved efficiently.
文摘The electrochemical characteristics and crystal structure of metal hydride electrode of AB_(3.5)-type alloy was studied. The electrochemical properties of the metal hydride electrode were investigated at room temperature and -30 ℃. The partial substitution of Ni by Al element causes an expansion of the lattice cell and increases the specific capacity and rate discharge ability of the alloy.
基金Project(2006AA11A151) supported by the National Hi-Tech Research and Development Program of China
文摘The Co(Ⅲ)-coated spherical nickel hydroxide powder is optimum as positive electrode of high power Ni-MH battery because of its excellent property. But the performances at high temperature(above 50 ℃) is still not satisfied. In the present paper,the effect of element erbium,used as additive by different methods to prepare positive electrode,on the high temperature performances of the Ni-MH batteries is studied. It is found that the charge acceptance ability of the spherical Ni(OH)2 electrode with element erbium as additive is improved. The discharge capacities of Ni(OH)2 coated with 1%(atomic fraction) Er(OH)3 and mechanically added with 1%(atomic fraction) Er2O3 at 1C are 12.6% and 11.7%,respectively,higher than those of the samples without erbium at 70 ℃.
基金Supported by the National Natural Science Foundation of China（Nos. 51771164, 51571173 and 51701175）.
文摘We reported the effects of annealing temperatures on microstructure and electrochemical properties of perovskite-type oxide LaFeO3 prepared by stearic acid combustion method. X-Ray diffraction（XRD） patterns show that the annealed LaFeO3 powder has orthorhombic structure. Scanning electron microscopy（SEM） and transmission electron microscopy（TEM） images show the presence of homogeneously dispersed, less aggregated, and small crystals（30--40 nm） at annealing temperatures of 500 and 600 ℃. However, as the annealing temperature was increased to 700 and 800 ℃, the crystals began to combine with each other and grew into further larger crystals（90--100 nm）. The electrochemical performance of the annealed oxides was measured at 60 ℃ using chronopotentiometry, potentiodynamic polarization, and cyclic voltammetry. As the annealing temperature increased, the discharge capacity and anti-corrosion ability of the oxide electrode first increased and then decreased, reaching the optimum values at 600 ℃, with a maximum discharge capacity of 563 mA-h/g. The better electrochemical performance of LaFeO3 annealed at 600℃ could be ascribed to their smaller and more homogeneous crysals.
