Catalytic characteristics of magnesium chloride supported rare earth catalyst system of Nd(OR) 3-n Cl n(n=0,1,2) in polymerization of butadiene was investigated.The result indicated that the ionic electronegativity of...Catalytic characteristics of magnesium chloride supported rare earth catalyst system of Nd(OR) 3-n Cl n(n=0,1,2) in polymerization of butadiene was investigated.The result indicated that the ionic electronegativity of magnesium and content of chlorine as measured in mumber of atom are important factors that affect the catalytic characteristics.展开更多
Supported rare earth catalysts were made from Nd(OiPr)3 and the chlorides of the elements of ⅡA groups which were used as supporters of the catalyst.In the study on the relationship between the composition of s...Supported rare earth catalysts were made from Nd(OiPr)3 and the chlorides of the elements of ⅡA groups which were used as supporters of the catalyst.In the study on the relationship between the composition of supporters and the polymerization activity of butadiene in the presence of the supported rare earth catalysts,it was found that the electronegativity of ⅡA groups elements had an obvious effect on the activity of supported catalysts that the activity and stereospecificity of the supported catalyst increased with the increasing of the electronegativity.This phenomenon was explained in terms of the interaction between the HOMO of the butadiene and the LUMO of the neodymium.展开更多
Based on the hexagonal crystallite model of graphite,the electrochemical characteristics of carbon atoms on the edge and basal plane were proposed by analyzing graphite crystal structure and bonds of carbon atoms in d...Based on the hexagonal crystallite model of graphite,the electrochemical characteristics of carbon atoms on the edge and basal plane were proposed by analyzing graphite crystal structure and bonds of carbon atoms in different sites.A spherical close-packed model for graphite particle was developed.The fractions of surface carbon atoms（SCA） and edge carbon atoms（ECA） were derived in the expression of crystallographic parameters and particle size,and the effects of ECA on the initial irreversible capacity and the mechanisms of action were analyzed and verified.The results show that the atoms on the edge are more active for electrochemical reactions,such as electrolyte decomposition and tendency to form stable bond with other atoms and groups.For the practical graphite particle,corresponding modifying factors were introduced to revise the difference in calculating results.The revised expression is suitable for the calculation of the fractions of SCA and ECA for carbon materials such as graphite,disordered carbon and modified graphite.展开更多
W-doped Li4TisO12 in the form of Li4Ti4.95W0.osO12 was firstly synthesized via solid state reaction. X-ray diffraction （XRD） and scanning electron microscope （gEM） were employed to characterize the structure and m...W-doped Li4TisO12 in the form of Li4Ti4.95W0.osO12 was firstly synthesized via solid state reaction. X-ray diffraction （XRD） and scanning electron microscope （gEM） were employed to characterize the structure and morphology of Li4Ti4.psW0.05Ol2. W-doping does not change the phase composition and particle morphology, while remarkably improves its cycling stability at high charge/discharge rate. Li4Ti4.95W0.05O12 exhibits an excellent rate capability with a reversible capacity of 131.2 mA.h/g at 10C and even 118.6 mA.h/g at 20C. The substitution of W for Ti site can enhance the electronic conductivity of Li4TisO12 via the generation of mixing Ti4＋/Ti3＋, which indicates that Li4Ti4.psW0.05O12 is promising as a high rate anode for the lithium-ion batteries.展开更多
Since the volume variation of silicon particles during cycling,the binding spots between Cu current collector and silicon anode raised to be one of the critical binding problems.In this work,an amino-modified Cu curre...Since the volume variation of silicon particles during cycling,the binding spots between Cu current collector and silicon anode raised to be one of the critical binding problems.In this work,an amino-modified Cu current collector(Cu^(*))is fabricated to tackle this issue.The amino groups on Cu^(*)surface increase its hydrophilicity,which is conducive to the curing process of aqueous slurry on its surface.Meanwhile,these amino groups can form abundant amide bonds with carboxyl groups from the adopted polyacrylic acid(PAA)binder.The combined action composed of the covalent bond and mechanical interlocking could reduce the contact loss inside the electrode.However,high concentration silane coupling agent treatment will weaken the surface roughness of Cu^(*)and weaken mechanical interlocking.What is more,the insulation of silane coupling agent reduces the conductivity of Cu and increases the impedance of battery.Considering the effect of silane coupling agent comprehensively,electrochemical performance of Cu^(*)-0.05%is best.展开更多
Co3O4/graphite composites were synthesized by precipitation of cobalt oxalate on the surface of graphite and pyrolysis of the precipitate, and the effects of graphite content and calcination temperature on the electro...Co3O4/graphite composites were synthesized by precipitation of cobalt oxalate on the surface of graphite and pyrolysis of the precipitate, and the effects of graphite content and calcination temperature on the electrochemical properties of the composites were investigated. The samples were characterized by thermogravimetry and differential thermal analysis （TG/DTA）, X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, cyclic voltammetry （CV）, electrochemical impedance spectroscopy （EIS） and charge/discharge measurements. With increasing the graphite content, the reversible capacity of the Co3O4/graphite composites decreases, while cycling stability improves dramatically, and the addition of graphite obviously decreases the average potential of lithium intercalation/deintercalation. The reversible capacity of the composites with 50% graphite rises from 583 to 725 mA-h/g as the calcination temperature increases from 300 to 500 ℃, and the Co304/graphite composites synthesized at 400 ℃ show the best cycling stability without capacity loss in the initial 20 cycles. peaks, corresponding to the lithium intercalaction/deintercalation for The CV profile of the composite presents two couples of redox graphite and Co3O4, respectively. EIS studies indicate that the electrochemical impedance decreases with increasing the graphite content.展开更多
Germanium based sulfides are potentially attractive as anode material for sodium ion batteries but rarely investigated. Herein, we firstly investigated Na^＋storage properties of pristine Cu2GeS3（PCGS） and found an ...Germanium based sulfides are potentially attractive as anode material for sodium ion batteries but rarely investigated. Herein, we firstly investigated Na^＋storage properties of pristine Cu2GeS3（PCGS） and found an effective strategy to improve its performance by a single lithiation/delithiation cycle obtaining ultrafine nanoparticle copper germanium sulfide（NCGS）. The lithiation/delithiation process leads to the formation of a stable Li-containing solid electrolyte interphase film and a significant improvement of sodiation kinetics. Therefore, the NCGS anode delivers favorable capacity retention and better rate capability compared with that of a PCGS whether in the half cell or in the full cell,showing great promise for energy storage application.展开更多
Highly crystalline and thermally stable pure multi-walled Ni3Si2O5（OH）4 nanotubes with a layered structure have been synthesized in water at a relatively low temperature of 200-210 ℃ using a facile and simple metho...Highly crystalline and thermally stable pure multi-walled Ni3Si2O5（OH）4 nanotubes with a layered structure have been synthesized in water at a relatively low temperature of 200-210 ℃ using a facile and simple method. The nickel ions between the layers could be reduced in situ to form size-tunable Ni nanocrystals, which endowed these nanotubes with tunable magnetic properties. Additionally, when used as the anode material in a lithium ion battery, the layered structure of the Ni3Si2O5（OH）4 nanotubes provided favorable transport kinetics for lithium ions and the discharge capacity reached 226.7 mA.h.g-1 after 21 cycles at a rate of 20 mA.g-1, Furthermore, after the nanotubes were calcined （600 ℃, 4 h） or reduced （180℃ 10 h）, the corresponding discharge capacities increased to 277.2 mA.h.g-1 and 308.5 mA.h.g-1, respectively.展开更多
Relying on a solvent thermal method, spherical Na2Li2Ti6O14 was synthesized. All samples prepared by this method are hollow and hierarchical structures with the size of about 2-3 μtm, which are assembled by many prim...Relying on a solvent thermal method, spherical Na2Li2Ti6O14 was synthesized. All samples prepared by this method are hollow and hierarchical structures with the size of about 2-3 μtm, which are assembled by many primary nanoparticles （-300nm）. Particle morphology analysis shows that with the increase of temperature, the porosity increases and the hollow structure becomes more obvious. Na2Li2Ti6Ol4 obtained at 800℃ exhibits the best electro- chemical performance among all samples. Charge-discharge results show that Na2Li2Ti6O14 prepared at 800℃ can delivers a reversible capacity of 220.1, 181.7, 161.6, 144.2, 118.1 and 97.2 mA h g-1 at 50, 140, 280, 560, 1400, 2800 mA g-1. How- ever, Na2Li2Ti6O4-bulk only delivers a reversible capacity of 187, 125.3, 108.3, 88.7, 69.2 and 54.8 mA h g-1 at the same current densities. The high electrochemical performances of the as-prepared materials can be attributed to the distinctive hollow and hierarchical spheres, which could effectively reduce the diffusion distance of Li ions, increase the con- tact area between electrodes and electrolyte, and buffer the volume changes during Li ion intercalation/deintercalation processes.展开更多
文摘Catalytic characteristics of magnesium chloride supported rare earth catalyst system of Nd(OR) 3-n Cl n(n=0,1,2) in polymerization of butadiene was investigated.The result indicated that the ionic electronegativity of magnesium and content of chlorine as measured in mumber of atom are important factors that affect the catalytic characteristics.
文摘Supported rare earth catalysts were made from Nd(OiPr)3 and the chlorides of the elements of ⅡA groups which were used as supporters of the catalyst.In the study on the relationship between the composition of supporters and the polymerization activity of butadiene in the presence of the supported rare earth catalysts,it was found that the electronegativity of ⅡA groups elements had an obvious effect on the activity of supported catalysts that the activity and stereospecificity of the supported catalyst increased with the increasing of the electronegativity.This phenomenon was explained in terms of the interaction between the HOMO of the butadiene and the LUMO of the neodymium.
基金Project (09001232) supported by the Doctoral Foundation of Henan University of Science and Technology,China
文摘Based on the hexagonal crystallite model of graphite,the electrochemical characteristics of carbon atoms on the edge and basal plane were proposed by analyzing graphite crystal structure and bonds of carbon atoms in different sites.A spherical close-packed model for graphite particle was developed.The fractions of surface carbon atoms（SCA） and edge carbon atoms（ECA） were derived in the expression of crystallographic parameters and particle size,and the effects of ECA on the initial irreversible capacity and the mechanisms of action were analyzed and verified.The results show that the atoms on the edge are more active for electrochemical reactions,such as electrolyte decomposition and tendency to form stable bond with other atoms and groups.For the practical graphite particle,corresponding modifying factors were introduced to revise the difference in calculating results.The revised expression is suitable for the calculation of the fractions of SCA and ECA for carbon materials such as graphite,disordered carbon and modified graphite.
文摘W-doped Li4TisO12 in the form of Li4Ti4.95W0.osO12 was firstly synthesized via solid state reaction. X-ray diffraction （XRD） and scanning electron microscope （gEM） were employed to characterize the structure and morphology of Li4Ti4.psW0.05Ol2. W-doping does not change the phase composition and particle morphology, while remarkably improves its cycling stability at high charge/discharge rate. Li4Ti4.95W0.05O12 exhibits an excellent rate capability with a reversible capacity of 131.2 mA.h/g at 10C and even 118.6 mA.h/g at 20C. The substitution of W for Ti site can enhance the electronic conductivity of Li4TisO12 via the generation of mixing Ti4＋/Ti3＋, which indicates that Li4Ti4.psW0.05O12 is promising as a high rate anode for the lithium-ion batteries.
基金Project(2019R01006)supported by the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang Province,ChinaProject(2018YFB0104300)supported by the National Key R&D Program of China。
文摘Since the volume variation of silicon particles during cycling,the binding spots between Cu current collector and silicon anode raised to be one of the critical binding problems.In this work,an amino-modified Cu current collector(Cu^(*))is fabricated to tackle this issue.The amino groups on Cu^(*)surface increase its hydrophilicity,which is conducive to the curing process of aqueous slurry on its surface.Meanwhile,these amino groups can form abundant amide bonds with carboxyl groups from the adopted polyacrylic acid(PAA)binder.The combined action composed of the covalent bond and mechanical interlocking could reduce the contact loss inside the electrode.However,high concentration silane coupling agent treatment will weaken the surface roughness of Cu^(*)and weaken mechanical interlocking.What is more,the insulation of silane coupling agent reduces the conductivity of Cu and increases the impedance of battery.Considering the effect of silane coupling agent comprehensively,electrochemical performance of Cu^(*)-0.05%is best.
基金Project(2007CB613607) supported by the National Basic Research Program of China Projects(2009FJ1002, 2009CK3062) supported by the Science and Technology Program of Hunan Province, China
文摘Co3O4/graphite composites were synthesized by precipitation of cobalt oxalate on the surface of graphite and pyrolysis of the precipitate, and the effects of graphite content and calcination temperature on the electrochemical properties of the composites were investigated. The samples were characterized by thermogravimetry and differential thermal analysis （TG/DTA）, X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, cyclic voltammetry （CV）, electrochemical impedance spectroscopy （EIS） and charge/discharge measurements. With increasing the graphite content, the reversible capacity of the Co3O4/graphite composites decreases, while cycling stability improves dramatically, and the addition of graphite obviously decreases the average potential of lithium intercalation/deintercalation. The reversible capacity of the composites with 50% graphite rises from 583 to 725 mA-h/g as the calcination temperature increases from 300 to 500 ℃, and the Co304/graphite composites synthesized at 400 ℃ show the best cycling stability without capacity loss in the initial 20 cycles. peaks, corresponding to the lithium intercalaction/deintercalation for The CV profile of the composite presents two couples of redox graphite and Co3O4, respectively. EIS studies indicate that the electrochemical impedance decreases with increasing the graphite content.
基金National Natural Science Foundation of China (51502319)Shandong Provincial Natural Science Foundation (BS2015CL014)the Think-Tank Mutual Fund of Qingdao Energy Storage Industry Scientific Research and Qingdao Key Lab of Solar Energy Utilization and Energy Storage Technology
文摘Germanium based sulfides are potentially attractive as anode material for sodium ion batteries but rarely investigated. Herein, we firstly investigated Na^＋storage properties of pristine Cu2GeS3（PCGS） and found an effective strategy to improve its performance by a single lithiation/delithiation cycle obtaining ultrafine nanoparticle copper germanium sulfide（NCGS）. The lithiation/delithiation process leads to the formation of a stable Li-containing solid electrolyte interphase film and a significant improvement of sodiation kinetics. Therefore, the NCGS anode delivers favorable capacity retention and better rate capability compared with that of a PCGS whether in the half cell or in the full cell,showing great promise for energy storage application.
基金This work was supported by the Natural Science Foundation of China （No. 20725102）, the Fok Ying Tung Education Foundation （No. 111012）, and the State Key Project of Fundamental Research for Nanoscience and Nanotechnology （Nos. 2011CB932402, 2007CB310501, and 2011CB935704）.
文摘Highly crystalline and thermally stable pure multi-walled Ni3Si2O5（OH）4 nanotubes with a layered structure have been synthesized in water at a relatively low temperature of 200-210 ℃ using a facile and simple method. The nickel ions between the layers could be reduced in situ to form size-tunable Ni nanocrystals, which endowed these nanotubes with tunable magnetic properties. Additionally, when used as the anode material in a lithium ion battery, the layered structure of the Ni3Si2O5（OH）4 nanotubes provided favorable transport kinetics for lithium ions and the discharge capacity reached 226.7 mA.h.g-1 after 21 cycles at a rate of 20 mA.g-1, Furthermore, after the nanotubes were calcined （600 ℃, 4 h） or reduced （180℃ 10 h）, the corresponding discharge capacities increased to 277.2 mA.h.g-1 and 308.5 mA.h.g-1, respectively.
基金supported by the National Natural Science Foundation of China (21301052 and 51404002)Natural Science Foundation of Heilongjiang Province (E2016056)+2 种基金Specialized Research Fund for the Doctoral Program of Higher Education (20132301120001)Postdoctoral Science-Research Developmental Foundation of Heilongjiang Province (LBH-Q13138)Applied Technology Research and Development Program of Harbin (2015RAQXJ032)
文摘Relying on a solvent thermal method, spherical Na2Li2Ti6O14 was synthesized. All samples prepared by this method are hollow and hierarchical structures with the size of about 2-3 μtm, which are assembled by many primary nanoparticles （-300nm）. Particle morphology analysis shows that with the increase of temperature, the porosity increases and the hollow structure becomes more obvious. Na2Li2Ti6Ol4 obtained at 800℃ exhibits the best electro- chemical performance among all samples. Charge-discharge results show that Na2Li2Ti6O14 prepared at 800℃ can delivers a reversible capacity of 220.1, 181.7, 161.6, 144.2, 118.1 and 97.2 mA h g-1 at 50, 140, 280, 560, 1400, 2800 mA g-1. How- ever, Na2Li2Ti6O4-bulk only delivers a reversible capacity of 187, 125.3, 108.3, 88.7, 69.2 and 54.8 mA h g-1 at the same current densities. The high electrochemical performances of the as-prepared materials can be attributed to the distinctive hollow and hierarchical spheres, which could effectively reduce the diffusion distance of Li ions, increase the con- tact area between electrodes and electrolyte, and buffer the volume changes during Li ion intercalation/deintercalation processes.
