TiAlCrN coatings were deposited by means of vacuum cathodic arc ion plating technique on TC 11 (Ti-6.5Al-3.5Mo-1.5Zr-0.3Si) titanium alloy substrates. The composition, phase structure, mechanical performance, and ox...TiAlCrN coatings were deposited by means of vacuum cathodic arc ion plating technique on TC 11 (Ti-6.5Al-3.5Mo-1.5Zr-0.3Si) titanium alloy substrates. The composition, phase structure, mechanical performance, and oxidation-resistance of the nivide coatings were investi- gated by scanning electron microscopy (SEM), atomic force microscope (AFM), X-ray diffraction (XRD), auger electron spectroscopy (AES), and X-ray photoelectron microscopy (XPS). A new process for preparing protective coatings of the titanium alloy is successfully ac- quired. The experimental results indicate that the added element chromium in the TiAlN coatings make a contribution to form the (220) pre- ferred direction. The phases of the coatings are composed of (Ti,Al)N and (Ti,Cr)N. After 700~C and 800~C oxidation, AES analysis shows that the diffusion distribution of the TiAlCrN coatings emerges a step shape. From the outside to the inner, the concentrations of O, Al, and Cr reduce, but those of Ti and N increase. The Al-rich oxide is formed on the surface of the coatings, and the mixed structure of Ti-rich and Cr-rich oxides is formed in the internal layer. The oxidation resistance of the TiAlCrN coatings is excellent at the range of 700 to 800~C. Adhesion wear is the dominant mechanical characteristic for the titanium alloy at room temperature, and the protective coatings with high hardness can improve the mechanical properties of the titanium alloy. The wear resistance of the TC 11 alloy is considerably improved by the TiAlCrN coatings.展开更多
A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of allo...A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of alloy elements, and lithium intercalation/de-intercalation behaviors of the fabricated films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), electron probe microanalyzer (EPMA), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma atomic emission spectrometry (ICP), cyclic voltammetry (CV), and galvanostatic charge/discharge (GC) measurements. It is found that the lithium intercalation/de-intercalation behavior of the Sn film can be significantly improved by its composite with graphite. With cycling, the discharge capacity of the Sn film without composite changes from 570 mAh/g of the 2nd cycle to 270 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 90% and 95%. Nevertheless, the discharge capacity of the composite Sn/C film changes from 575 mAh/g of the 2nd cycle to 515 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 95% and 100%. The performance improvement of tin by its composite with graphite is ascribed to the retardation of the bulk tin cracking from volume change during lithium intercalation and de-intercalation, which leads to the pulverization of tin.展开更多
TiO2-coated SnO2 (TCS) hollow spheres, which are new anode materials for lithium ion (Li-ion) batteries, were prepared and characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transm...TiO2-coated SnO2 (TCS) hollow spheres, which are new anode materials for lithium ion (Li-ion) batteries, were prepared and characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), and galvanostatic charge/discharge tests. The results obtained from XRD, SEM, and TEM show that TiO2 can be uniforrrdy coated on the surface of SnO2 hollow spheres with the assistance of anionic surfactant. The cyclic voltammograms indicate that both TiO2 and SnO2 exhibit the activity for Li-ion storage. The charge/discharge tests show that the prepared TCS hollow spheres have a higher reversible coulomb efficiency and a better cycling stability than the uncoated SnO2 hollow spheres.展开更多
Ti0.5Al0.5N coatings were deposited on TC11(Ti-6.5Al-3.5Mo-1.5Zr-0.3Si) and silicon substrates using a cathode arc ion-plating system.The microstructure, composition, phase structure, and oxidation-resistance of the...Ti0.5Al0.5N coatings were deposited on TC11(Ti-6.5Al-3.5Mo-1.5Zr-0.3Si) and silicon substrates using a cathode arc ion-plating system.The microstructure, composition, phase structure, and oxidation-resistance of the alloys and nitride coatings were investigated by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, Auger electron spectroscopy, and thermal analyzer.The results show that the oxidation resistance of the titanium alloy is relatively limited;the compound structures of Ti mixed with Al oxides are formed during the heating process.The phases of the Ti0.5Al0.5N coatings are composed of a TiN solid solution phase.The oxidation kinetics obeys the parabolic law.During the oxidation process, the selective oxidation of Al occurs, thus protecting the underlying coating and substrate.展开更多
The stoichiometric alloy MlB5.0 and the hypo-stoichiometric alloy MlB4.85 were prepared by twin-roller rapid quenching process, and their structure and electrochemical properties were studied. The results of XRD show ...The stoichiometric alloy MlB5.0 and the hypo-stoichiometric alloy MlB4.85 were prepared by twin-roller rapid quenching process, and their structure and electrochemical properties were studied. The results of XRD show that both of the alloys have a typical single-phase hexagonal CaCus-type structure. The cell volume of the hylpo-stoichiometric alloy M1B4.85 is slightly larger than that of the stoichiometric alloy M1B5.0, although its lattice constant cla is smaller. Under 2 C discharging rate, i.e. 640 mA/g, the M1B4.85 has a discharge capacity of 320 mAh/g, which is higher than that of the M1Bs.o, 312 mAh/g. Nevertheless, the capacities of the M1B4.85 and the M1Bs.o decline 24.7% and 20.2% after 400 cycles, respectively. The relationship of electrochemical performances of the alloys with their structures is discussed.展开更多
Based on density functional theory (DFT) of the first-principle for the cathode materials of lithium ion battery, the electronic structures of Li(Fe1-xMex)PO4 (Me = Ag/Mn, x = 0―0.40) are calculated by plane wave pse...Based on density functional theory (DFT) of the first-principle for the cathode materials of lithium ion battery, the electronic structures of Li(Fe1-xMex)PO4 (Me = Ag/Mn, x = 0―0.40) are calculated by plane wave pseudo-potential method using Cambridge serial total energy package (CASTEP) program. The calculated results show that the Fermi level of mixed atoms Fe1-xAgx moves into its conduction bands (CBs) due to the Ag doping. The Li(Fe1-xAgx)PO4 system displays the periodic direct semiconductor characteristic with the increase of Ag-doped concentration. However, for Fe1-xMnx mixed atoms, the Fermi level is pined at the bottom of conduction bands (CBs), which is ascribed to the interaction be-tween Mn(3d) electrons and Fe(4s) electrons. The intensity of the partial density of states (PDOS) near the bottom of CBs becomes stronger with the increase of Mn-doped concentration. The Fermi energy of the Li(Fe1-xMnx)PO4 reaches maximum at x = 0.25, which is consistent with the experimental value of x = 0.20. The whole conduction property of Mn-doped LiFePO4 is superior to that of Ag-doped LiFePO4 cathode material, but the structural stability is reverse.展开更多
In this work, based on First-principle plane wave pseudo-potential method, we have carried out an in-depth study on the possible dead lithium phase of Sn-Zn alloy as anode materials for lithium ion batteries. Through ...In this work, based on First-principle plane wave pseudo-potential method, we have carried out an in-depth study on the possible dead lithium phase of Sn-Zn alloy as anode materials for lithium ion batteries. Through investigation, we found that the phases LixSn4Zn4(x = 2, 4, 6, 8) contributed to re-versible capacity, while the phases LixSn4Zn8-(x-4)(x = 4.74, 7.72) led to capacity loss due to high forma-tion energy, namely, they were the dead lithium phases during the charge/discharge process. And we come up with a new idea that stable lithium alloy phase with high lithiation formation energy (dead lithium phase) can also result in high loss of active lithium ion, besides the traditional expression that the formation of solid electrolyte interface film leads to high capacity loss.展开更多
The electronic structure and electrochemical parameters of ternary NiSn0.5Ti0.5 phase are investigated by plane-wave pseudopotential method of the first-principle.The interstitial sites are firstly filled with lithium...The electronic structure and electrochemical parameters of ternary NiSn0.5Ti0.5 phase are investigated by plane-wave pseudopotential method of the first-principle.The interstitial sites are firstly filled with lithium atoms,and then the substitution for Ni sites occurs.The results show that the Fermi level of lithium-intercalated phase goes up with the increasing lithium concentration.These interactions of M-M covalent bonds (M=Ni,Sn,Ti) become weak,while Li-M bonds are found to increase.NiSn 0.5Ti0.5 phase is characterized with high theoretical capacity and low voltage of lithium-intercalation.The obvious volume effect from 77.15%to 189.94% would lead to the failure of the electrode material,and therefore the NiSn0.5Ti0.5 compound should be limited as low as possible in multi-element Sn-based alloy.展开更多
基金This study is financially supported by the National Natural Science Foundation of China(No.50271019)the Scientific Planning Project of Guangzhou City(No.2003Z2-D2071)the Natural Science Foundation of Guangdong Province,China(No.05100534).
文摘TiAlCrN coatings were deposited by means of vacuum cathodic arc ion plating technique on TC 11 (Ti-6.5Al-3.5Mo-1.5Zr-0.3Si) titanium alloy substrates. The composition, phase structure, mechanical performance, and oxidation-resistance of the nivide coatings were investi- gated by scanning electron microscopy (SEM), atomic force microscope (AFM), X-ray diffraction (XRD), auger electron spectroscopy (AES), and X-ray photoelectron microscopy (XPS). A new process for preparing protective coatings of the titanium alloy is successfully ac- quired. The experimental results indicate that the added element chromium in the TiAlN coatings make a contribution to form the (220) pre- ferred direction. The phases of the coatings are composed of (Ti,Al)N and (Ti,Cr)N. After 700~C and 800~C oxidation, AES analysis shows that the diffusion distribution of the TiAlCrN coatings emerges a step shape. From the outside to the inner, the concentrations of O, Al, and Cr reduce, but those of Ti and N increase. The Al-rich oxide is formed on the surface of the coatings, and the mixed structure of Ti-rich and Cr-rich oxides is formed in the internal layer. The oxidation resistance of the TiAlCrN coatings is excellent at the range of 700 to 800~C. Adhesion wear is the dominant mechanical characteristic for the titanium alloy at room temperature, and the protective coatings with high hardness can improve the mechanical properties of the titanium alloy. The wear resistance of the TC 11 alloy is considerably improved by the TiAlCrN coatings.
基金the National Nature Science Foundation of China (Nos. 50771046 and 20373016) the Natural Science Foundation of Guangdong Province (No. 05200534)the Key Projects of Guangdong Province and Guangzhou City, China (Nos. 2006A10704003 and 2006Z3-D2031)
文摘A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of alloy elements, and lithium intercalation/de-intercalation behaviors of the fabricated films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), electron probe microanalyzer (EPMA), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma atomic emission spectrometry (ICP), cyclic voltammetry (CV), and galvanostatic charge/discharge (GC) measurements. It is found that the lithium intercalation/de-intercalation behavior of the Sn film can be significantly improved by its composite with graphite. With cycling, the discharge capacity of the Sn film without composite changes from 570 mAh/g of the 2nd cycle to 270 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 90% and 95%. Nevertheless, the discharge capacity of the composite Sn/C film changes from 575 mAh/g of the 2nd cycle to 515 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 95% and 100%. The performance improvement of tin by its composite with graphite is ascribed to the retardation of the bulk tin cracking from volume change during lithium intercalation and de-intercalation, which leads to the pulverization of tin.
基金financially supported by the National Natural Science Foundation of China (No.20873046)the Specialized Research Fund for the Doctoral Program of HigherEducation (No.200805740004)Natural Science Foundation of Guangdong Province (No.10351063101000001)
文摘TiO2-coated SnO2 (TCS) hollow spheres, which are new anode materials for lithium ion (Li-ion) batteries, were prepared and characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), and galvanostatic charge/discharge tests. The results obtained from XRD, SEM, and TEM show that TiO2 can be uniforrrdy coated on the surface of SnO2 hollow spheres with the assistance of anionic surfactant. The cyclic voltammograms indicate that both TiO2 and SnO2 exhibit the activity for Li-ion storage. The charge/discharge tests show that the prepared TCS hollow spheres have a higher reversible coulomb efficiency and a better cycling stability than the uncoated SnO2 hollow spheres.
文摘Ti0.5Al0.5N coatings were deposited on TC11(Ti-6.5Al-3.5Mo-1.5Zr-0.3Si) and silicon substrates using a cathode arc ion-plating system.The microstructure, composition, phase structure, and oxidation-resistance of the alloys and nitride coatings were investigated by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, Auger electron spectroscopy, and thermal analyzer.The results show that the oxidation resistance of the titanium alloy is relatively limited;the compound structures of Ti mixed with Al oxides are formed during the heating process.The phases of the Ti0.5Al0.5N coatings are composed of a TiN solid solution phase.The oxidation kinetics obeys the parabolic law.During the oxidation process, the selective oxidation of Al occurs, thus protecting the underlying coating and substrate.
基金[This project was supported by the National Natural Science Foundation of China (No. 20373016), the Key Project of In-ternational Science and Technology Cooperation of MOST of China (No. 2005DFA60580), the Key Project of Guangdong Province (No. 2005B50101003), and the Excellent Young Teachers Program of MOE of China.]
文摘The stoichiometric alloy MlB5.0 and the hypo-stoichiometric alloy MlB4.85 were prepared by twin-roller rapid quenching process, and their structure and electrochemical properties were studied. The results of XRD show that both of the alloys have a typical single-phase hexagonal CaCus-type structure. The cell volume of the hylpo-stoichiometric alloy M1B4.85 is slightly larger than that of the stoichiometric alloy M1B5.0, although its lattice constant cla is smaller. Under 2 C discharging rate, i.e. 640 mA/g, the M1B4.85 has a discharge capacity of 320 mAh/g, which is higher than that of the M1Bs.o, 312 mAh/g. Nevertheless, the capacities of the M1B4.85 and the M1Bs.o decline 24.7% and 20.2% after 400 cycles, respectively. The relationship of electrochemical performances of the alloys with their structures is discussed.
基金the National Natural Science Foundation of China (Grant No. 50771046)the Natural Science Foundation of Guangdong Province (Grant No. 05200534)the Key Projects of Guangdong Province and Guangzhou City (Grant Nos. 2006A10704003 and 2006Z3-D2031)
文摘Based on density functional theory (DFT) of the first-principle for the cathode materials of lithium ion battery, the electronic structures of Li(Fe1-xMex)PO4 (Me = Ag/Mn, x = 0―0.40) are calculated by plane wave pseudo-potential method using Cambridge serial total energy package (CASTEP) program. The calculated results show that the Fermi level of mixed atoms Fe1-xAgx moves into its conduction bands (CBs) due to the Ag doping. The Li(Fe1-xAgx)PO4 system displays the periodic direct semiconductor characteristic with the increase of Ag-doped concentration. However, for Fe1-xMnx mixed atoms, the Fermi level is pined at the bottom of conduction bands (CBs), which is ascribed to the interaction be-tween Mn(3d) electrons and Fe(4s) electrons. The intensity of the partial density of states (PDOS) near the bottom of CBs becomes stronger with the increase of Mn-doped concentration. The Fermi energy of the Li(Fe1-xMnx)PO4 reaches maximum at x = 0.25, which is consistent with the experimental value of x = 0.20. The whole conduction property of Mn-doped LiFePO4 is superior to that of Ag-doped LiFePO4 cathode material, but the structural stability is reverse.
基金Supported by the National Natural Science Foundation of China (Grant No. 50771046)Natural Science Foundation of Guangdong Province (Grant No.05200534)+1 种基金Key Projects of Guangdong Province and Guangzhou City (Grant Nos. 2006A10704003 and 2006Z3-D2031)China Postdoctoral Science Foundation (Project No. 20080440764)
文摘In this work, based on First-principle plane wave pseudo-potential method, we have carried out an in-depth study on the possible dead lithium phase of Sn-Zn alloy as anode materials for lithium ion batteries. Through investigation, we found that the phases LixSn4Zn4(x = 2, 4, 6, 8) contributed to re-versible capacity, while the phases LixSn4Zn8-(x-4)(x = 4.74, 7.72) led to capacity loss due to high forma-tion energy, namely, they were the dead lithium phases during the charge/discharge process. And we come up with a new idea that stable lithium alloy phase with high lithiation formation energy (dead lithium phase) can also result in high loss of active lithium ion, besides the traditional expression that the formation of solid electrolyte interface film leads to high capacity loss.
基金supported by the National Natural Science Foundation of China(50771046)
文摘The electronic structure and electrochemical parameters of ternary NiSn0.5Ti0.5 phase are investigated by plane-wave pseudopotential method of the first-principle.The interstitial sites are firstly filled with lithium atoms,and then the substitution for Ni sites occurs.The results show that the Fermi level of lithium-intercalated phase goes up with the increasing lithium concentration.These interactions of M-M covalent bonds (M=Ni,Sn,Ti) become weak,while Li-M bonds are found to increase.NiSn 0.5Ti0.5 phase is characterized with high theoretical capacity and low voltage of lithium-intercalation.The obvious volume effect from 77.15%to 189.94% would lead to the failure of the electrode material,and therefore the NiSn0.5Ti0.5 compound should be limited as low as possible in multi-element Sn-based alloy.