Electrochemical behavior of CoCl2 in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

The electrochemical behavior of CoCl2 in 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6) was investigated by cyclic voltammetry. The cyclic voltammograms were obtained from electrochemical measurement under different temperatures, and the reversible behavior for Co2 /Co3 redox couple on glassy carbon electrode in [bmim]PF6 was confirmed by the characteristic of the peak currents. The diffusion coefficients (about 10-11m2/s) of Co2 in [bmim]PF6 under different temperatures were evaluated from the dependence of the peak current density on the potential scan rates in cyclic voltammograms. It is found that the diffusion coefficient increases with increasing temperature. Diffusion activation energy of Co2 in [bmim]PF6 is also calculated to be 23.4kJ/mol according to the relationship between diffusion coefficient and temperature.     

Electrochemical behavior of K3Fe（CN）6 in water-in-oil microemulsion

A water-in-oil (W/O) microemulsion composed of Triton X-100, n-hexanol, n-hexane and water solution with hydrochloric acid was prepared. K₃Fe(CN)₆ was added in as a water-soluble electroactive probe, and its electrochemical behavior was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is found that the H⁺ concentration of the water phase has a great effect on the conductivity of the W/O microemulsion, and hence influences the electrochemical behavior of K₃Fe(CN)₆. When the pH value of water phase is about 7, the electrical conductivity of the W/O microemulsion is only 1.2×10⁻⁶ S/cm, and K₃Fe(CN)₆ almost cannot react at the glassy carbon electrode. But when the H⁺ concentration is more than 3 mol/L, the W/O microemulsion has a good electrical conductivity and K₃Fe(CN)₆ shows good electrochemical performance in it. The results of CV and EIS studies indicate that the electrochemical behavior of Fe(CN)₆ ³⁻/Fe(CN)₆ ⁴⁻ in the W/O microemulsion is different from that in the aqueous solution. This may be due to the unique liquid structure of the W/O microemulsion and the unique mass transfer in the W/O microemulsion. Foundation item: Projects(20673036, J0830415) supported by the National Natural Science Foundation of China; Projects(05JT1026, 2007JT2013) supported by the Science Technology Project of Hunan Province, China     

Cathodic behavior of molten CaCl2-CaO and CaCl2-NaCl-CaO

The cathodic behavior of molten CaCl2,CaCl2-CaO and equimolar CaCl2-NaCl-CaO was studied by cyclic voltammograms and constant potential polarization at temperatures of 1123 to 1173 K on molybdenum and titanium electrodes.The diffusion coefficient of Ca2+ (CaO)in molten CaCl2-CaO was calculated from the linear relationship between the square root of scan rate and the peak current density.The deposition potentials and the potential temperature coefficient of CaO in molten CaCl2-0.5mo1% CaO and CaCl2-NaCl-0.5mol%CaO were also obtained from their cyclic voltammograms.The result shows that CaO is more easily reduced than CaCl2.The addition of NaCI in molten CaCl2-CaO induces the underpotential electrodeposition of CaO.     

Mechanism of zinc electroplating in alkaline zincate solution

The cathodic deposition properties and mechanism of Zn in alkaline zincate solution were studied by electrochemical techniques. The results show that Zn2 exists in the alkaline solution in the form of Zn(OH)42-. The apparent activation energy of the electrode reaction is 38.93 kJ/mol, which indicates that the discharge of Zn(OH)42- on cathode is controlled by electrochemical polarization, and accompanied by a preceding chemical reaction. The diffusion coefficient of Zn(OH)42- is 2.452×10-6 cm2/s. Zn(OH)2 is the species directly discharged on the cathode surface. Based on the above results the mechanism of zinc electroplating in alkaline zincate solution was put forward. The discharged species is Zn(OH)2 formed from the preceding chemical reaction, which becomes Zn(OH)ad when gaining one electron, and then gaining the second electron to become Zn. The first electron gaining step is rate determining one.     

High temperature cyclic oxidation behavior of Y2O3-ZrO2 thermal barrier coatings irradiated by high-intensity pulsed ion beam

The high-temperature oxidation resistance behavior of 7% (mass fraction) Y₂O₃-ZrO₂ thermal barrier coatings (TBCs) irradiated by high-intensity pulsed ion beam (HIPIB) was investigated under the cyclic oxidation condition of 1 050 °C and 1 h. The columnar grains in the TBCs disappear after the HIPIB irradiation at ion current densities of 100–200 A/cm² and the irradiated surface becomes smooth and densified after remelting and ablation due to the HIPIB irradiation. The thermally grown oxide (TGO) layer thickness of the irradiated TBCs is smaller than that of the original TBCs. After 15 cycles, the mass gains of the original TBCs and those irradiated by ion current densities of 100 and 200 A/cm² due to the oxidation are found to be 0.8–0.9, 0.6–0.7, and 0.3–0.4 mg/cm², respectively. The inward diffusion of oxygen through the irradiated TBCs is significantly impeded by the densified top layer formed due to irradiation, which is the main reason for the improved overall oxidation resistance of the irradiated TBCs. Foundation item: Projects supported by The 2nd Stage of Brain Korea and Korea Research Foundation     

Preparation and electrochemical studies of Y-doped LiVPO<Subscript>4</Subscript>F cathode materials for lithium-ion batteries

Y-doped LiVPO₄F cathode materials were prepared by a carbothermal reduction(CTR) process. The properties of the Y-doped LiVPO₄F samples were investigated by X-ray diffraction (XRD) and electrochemical measurements. XRD studies show that the Y-doped LiVPO₄F samples have the same triclinic structure as the undoped LiVPO₄F. The Li extraction/insertion performances of Y-doped LiVPO₄F samples were investigated through charge/discharge, cyclic voltammogram (CV), and electrochemical impedance spectra(EIS). The optimal doping content of Y is x=0.04 in LiY _x V_1−x PO₄F system. The Y-doped LiVPO₄F samples show a better cyclic ability. The electrode reaction reversibility is enhanced, and the charge transfer resistance is decreased through the Y-doping. The improved electrochemical performances of the Y-doped LiVPO₄F cathode materials are attributed to the addition of Y³⁺ ion by stabilizing the triclinic structure. Funded by the Sponsor Teams for Innovation in the Construction of Talent Highlands in Guangxi Institutions of Higher Learning(GuiJiaoRen [2007]71), Guangxi Natural Science Foundation(No.0832259), the Research Funds of the Guangxi Key Laboratory of Environmental Engineering, Protection and Assessment Program to Sponsor Teams for Innovation in the Construction of Talent Highlands in Guangxi Institutions of Higher Learning(GuiJiaoRen [2007]71)     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi_0.45Co_0.10Mn_0.45O₂ was synthesized from Li₂CO₃ and a triple oxide of nickel, cobalt and manganese at 950 °C in air. The structures and characteristics of LiNi_0.45Co_0.10Mn_0.45O₂, LiCoO₂ and LiMn₂O₄ were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi_0.45Co_0.10Mn_0.45O₂ has a layered structure with hexagonal lattice. The commercial LiCoO₂ has sphere-like appearance and smooth surfaces, while the LiMn₂O₄ and LiNi_0.45Co_0.10Mn_0.45O₂ consist of cornered and uneven particles. LiNi_0.45Co_0.10Mn_0.45O₂ has a large discharge capacity of 140.9 mA · h/g in practical lithium ion battery, which is 33.4% and 2.8% above that of LiMn₂O₄ and LiCoO₂, respectively. LiCoO₂ and LiMn₂O₄ have higher discharge voltage and better rate-capability than LiNi_0.45Co_0.10Mn_0.45O₂. All the three cathodes have excellent cycling performance with capacity retention of above 89.3% at the 250th cycle. Batteries with LiMn₂O₄ or LiNi_0.45Co_0.10Mn_0.45O₂ cathodes show better safety performance under abusive conditions than those with LiCoO₂ cathodes. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China; Project(2005037698) supported by the Postdoctoral Science Foundation of China     

Lithium Instertion in poly (ethylene oxide )/MoO3 Xerogel Nanocomposite Films

The nanocomposite films were prepared by direct intercalation of poly (ethylene oxide) and PEO into MoO3 xerogel via sol-gel route,The electrochromic behavior and the chemical conditionws of Li^ ions were investigated by cyclic voltammograms,UV-visible spectral transmittance and XPS,The tesults show that the cycling efficiency and the reversibility of insertion/extraciton of Li^ ions in (PEO)1 MoO3 .nH2O nanocomposite film were improved.The intercalation of PEO into MoO3 xerogel modulated the wavelength range of electrochromism and enhanced the electrochromic efficiney,Two different chemical conditions of Li^ ions existing in the interlayer and interstitial positions of MoO3 lattice were observed in MoO3 XEROGEL AND (PEO)1 MoO3.nH2O naocomposite films.     

Dynamics of electrodeposition of tetraethylthioram disulphide (TETD) on pyrite surface

Ｄｉｅｔｈｙｌｄｉｔｈｉｏｃａｒｂａｍａｔｅ(ＤＤＴＣ)ｉｓｏｎｅｏｆｔｈｅｍｏｓｔｆｒｅｑｕｅｎｔｌｙｕｓｅｄｃｏｌｌｅｃｔｏｒｆｏｒｆｌｏｔａｔｉｏｎｏｆｈｅａｖｙ ｍｅｔａｌｓｕｌｆｉｄｅｍｉｎｅｒａｌｓ,ｓｕｃｈａｓｇａｌｅｎａ ,ｃｈａｌｃｏｐｙｒｉｔｅａｎｄｊａｍｅｓｏｎｉｔｅ ,ａｎｄｓｈｏｗｓｓｔｒｏｎｇｓｅ ｌｅｃｔｉｖｉｔｙ[1] .ＩｔｉｓｒｅｐｏｒｔｅｄｔｈａｔＤＤＴＣｉｓａｐｏｗｅｒｆｕｌｃｏｌｌｅｃｔｏｒｆｏｒｇａｌｅｎａａｎｄｖｅｒｙｓｅｌｅｃｔｉｖｅａｇａｉｎｓｔｐｙｒｉｔｅｉ…     

Structural characteristics of spherical Ni（OH）2 and its charge／discharge process mechanism

Spherical Ni(OH)2 particles were prepared by an aqueous solution precipitation route. The structure of spherical Ni(OH)2 was investigated by scanning electron microscopy and transmission electron microscopy and compared with that of traditional Ni(OH)2. The results show that the spherical nickel hydroxide consists of Ni(OH)2 spheres with a reticulate structure of platelet-like, which is almost arranged radially and the crystalline grains intervene and connect with each other to form a three-dimensional net. The spherical Ni(OH)2 particle is full of pores,crannies between cleave planes. It is supposed that this structure is beneficial to the structural stability for the spherical particles during the charge/discharge processes and can improve the cycle life of the electrode; the pores and the crannies in spherical particles can shorten the proton diffusion distance and speed its velocity, which may result in that the local polarization is lowered. The electrochemical performances of the spherical Ni(OH)2 are improved by enhancing the conducting properties of the crystalline lattice due to its quick proton diffusion.     

Synthesis of Lithium-cobalt Oxides by Sol-gel Method and their Cathodical Discharge Behavior at 500

Three kinds of lithium-cobalt oxides with lithium to cobalt atomic ratios of 0.6, 0.8 and 1.0 respectively were prepared using nitrates and citric acid by sol-gel process. During the baking of the dry-gel powder, two exothermic peaks occur, followed by the formation of Li₂O and Co₃O₄ and then the combination of LiCoO₂, which is testified by DTA and XRD. The powder formed from an alkaline sol is finer than that from the acidic one. There are a single phase intercalation of lithium ion and an electrochemical reduction reaction for higher-valence cobalt ion when simulating the discharging process of Li-B/LiCl-KCl/lithium-cobalt oxides at 500 °C, and the voltage and specific capacity are not sensitive to the initial ratios of lithium to cobalt. Foundation item: The Doctoral Foundation of the Education Ministry of China(No. 96053311) Biography of the first author: LI Zhi-you, born in 1968, majoring in materials for thermal battery.     

Synthesis and characterization of Mg3(PO4)2-coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode material for Li-ion battery

Mg₃(PO₄)₂-coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), charge/discharge cycling and differential scanning calorimeter (DSC). SEM analysis shows that Mg₃(PO₄)₂-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg₃(PO₄)₂-coating powder is homogeneous and has better layered structure than the bare one. Mg₃(PO₄)₂-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg₃(PO₄)₂-coated sample at 55 °C was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg₃(PO₄)₂-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells: the Mg₃(PO₄)₂ coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li_1.05Ni_1/3Mn_1/3Co_1/3O₂. Funded by the National Natural Science Foundation of China (No. 20273047)     

Electrochemical kinetics of gold dissolving in alkaline thiourea solution

1 INTRODUCTIONEssentially , determination of electrode reac-tion mechanism is just the determination of thecourse of electrode reaction and the rate-determi-ning step[1 5]. Based on the previous results[6 11],gold dissolution mechanism undergoes the follow-ing courses in alkaline thiourea solution: adsorp-tion of thiourea on active points of electrode sur-face and formation of Au[SC(NH2)2]ads; chargetransfer fromactive gold atomto thiourea moleculeand formation of Au[SC(NH2)2]a+ds; Au-…     

Luminescent properties of BaO-La2O3-B2O3 glasses with dopant

The luminescent properties of glasses synthesized in air atmosphere by conventional high temperature process were stud{ed. The emissions spectra of Eu^2 and Eu^3 were observed in BaO-La2O3-B2O3-Eu2O3 glasses.The results show that the broad emission peaks at 430 nm correspond to 5d→4f emission transition of Eu^2 , the sharp emission peaks at 592, 616, 650 and 250 nm correspond to 5^D0→1Fj(j=1--4) emission transition of Eu^3 ,respectively, which indicates that the BaO-La2O3a-B2O3-Eu2O3 glass can convert ultraviolet and green omponents of sunlight into blue and red light so as to increase the intensity of blue and red light, respectively. The luminescent in--tensity of Eu^2 increases with increasing the molar ratio of Tb^3 in BaO-La2O3-B2O3-Eu2O3a-Tb4O3 glasses, whereas the luminescent intensity of Eua^3 decreases. So the luminescent intensity of Eu(Ⅲ,Ⅱ) is influenced by Tb^3 .These phenomena can be explained by electron transfer mechanism; Eu^3 (4f6) Tb^3 (4f^8)→Eu^2 (4f′) Tb^4 (4f′). Taking advantage of the luminescent properties of BaO-La2O3-B2O3-Eu2O3 glasses, light-conversion glass for agriculture can be produced.     

Influence on performance and structure of spinel LiMn2O4 for lithium-ion batteries by doping rare-earth Sm

The spinel LiMn₂O₄ used as cathode materials for lithium-ion batteries was synthesized by mechano-chemistry fluid activation process, and modified by doping rare-earth Sm. Thesting of X-ray diffraction, cyclic voltammograms, charge-discharge and SEM was carried out for LiMn₂O₄ cathode materials and the modified materials. The results show that the cathode materials doped rare earth Li _x Mn_2−y Sm _z O₄ (0.95⩽x⩽1.2, 0⩽y⩽0.3, 0⩽z⩽0.2) exhibit standard spinel structure, high reversibility of electrochemistry and excellent properties of charge-discharge. In EC: DMC(1 : 1)+1 mol/L LiPF₆ electrolyte with discharge capacity more than 130 mA · h/g, and its capacity is deteriorated less than 15% after 300 cycles at room temperature and less than 20% after 200 cycles at 55°C. At the same time, Crystal Field Theory was applied to explain the function and mechanism of doped rare earth element. Foundation item: Project (02JJY2081) supported by the Natural Science Foundation of Hunan Province     

Determination of isothermal section of Ag-Ti-Zr ternary system at 1 023 K

The isothermal section of Ag-Ti-Zr ternary system at 1023 K was determined by diffusion triple and electron probe microanalysis. The results indicate that four binary intermetallic phases of AgTi, AgTi2, AgZr and AgZr2 are found in Ag-Ti-Zr ternary system at 1 023 K. AgZr2 and AgTi2 form a continuous solid solution, namely Ag(Ti,Zr)2. Four three-phase regions: AgTi AgZr Ag, AgTi AgZr Ag (Ti, Zr)2, α-Zr β(Ti, Zr) Ag (Ti, Zr) 2 and α-Ti β(Ti, Zr) Ag (Ti, Zr)2 exist in the isothermal section. No ternary compound is observed.     

Al_2O_3包覆对富锂锰基正极材料Li_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2的电化学性能影响

采用水热法合成富锂三元正极材料,探究了最佳包覆比例下Al_2O_3包覆对材料的电化学性能影响.采用扫描电镜(SEM)和X射线衍射仪(XRD)表征了富锂三元正极材料的表面形貌和结构,通过循环伏安(CV)、交流阻抗(EIS)技术分析了材料电化学性的影响因素.结果表明,通过异丙醇铝水解制得了氧化铝包覆层,提高了材料的比容量,稳定了材料的结构.     

Synthesis of calixarenes and their extraction performance for ester catechins

A series of extractants (tert-butylcalix[6]arene, tert-butylcalix[8]arene and octeacetate of tert-butylcalix[8]arene) were synthesized, and their structures were identified by IR and 1H-NMR. The distribution behavior of ester catechins monomer in the aqueous and chloroform two-phase system containing one of calixarene was studied. The influences of different extractants, concentration of tert-butylcalix[8]arene and extraction temperature on the partition coefficients and the separation factors were investigated. The experiment results show that tert-butylcalix[8]arene is the best extractant that forms a more stable supramolecular compound with gallocatechin gallate (GCG) than with epigallocathechin gallate (EGCG) or epicatechin gallate (ECG). When the concentration of p-tert-butylcalix[8]arene is 3.79 mmol/L, the extraction temperature is 4 ℃, the partition coefficients of KGCG, KECG, KEGCG are 0.987, 0.629, 0.449,the separation factors of α1 and α2 are 1.450 and 1.596, respectively. The important factors influencing the extraction properties of calixarene are discovered to be its cavity size and hydrogen bonding.     

Microscopic phase-field simulation for coarsening behavior of L12 and DO22 phases of Ni75Cr x Al25? x alloy

Based on the microscopic phase-field dynamic model and the microelasticity theory, the coarsening behavior of L1₂ and DO₂₂ phases in Ni₇₅Cr _x Al_25−x alloy was simulated. The results show that the initial irregular shaped, randomly distributed L1₂ and DO₂₂ phases are gradually transformed into cuboidal shape with round corner, regularly aligned along directions [100] and [001], and highly preferential selected microstructure is formed during the later stage of precipitation. The elastic field produced by the lattice mismatch between the coherent precipitates and the matrix has a strong influence on the coarsening kinetics, and there is no linear relationship between the cube of the average size of precipitates and the aging time, which does not agree with the results predicted by the classical Lifshitz-Slyozov-Wagner. The coarsening processes of L1₂ and DO₂₂ phases are retarded in elastically constrained system. In the concurrent system of L1₂ and DO₂₂ phases, there are two types of coarsening modes: the migration of antiphase domain boundaries and the interphase Ostwald ripening. Foundation item: Project(50671084) supported by the National Natural Science Foundation of China; Project(20070420218) supported by China Postdoctoral Science Foundation     

Mechanism and behaviors of Cr3+-doped TiO2

TiO₂ powder and TiO₂ thin film on the surface of glazed ceramic tile were prepared by sol-gel method. The influences of different doping Cr³⁺ concentration on the photocatalytic activity of TiO₂ were discussed, UV-visible and X-ray diffraction analysis were used to test the performance of TiO₂ powder and film. The results indicate that photocatalytic activity of doping Cr³⁺-TiO₂ thin film is higher than that of powder, and the interaction between Cr³⁺-doped and substrate can greatly enhance the photocatalytic activity. The results of X-ray diffraction and photoabsorption show that the Cr³⁺-doped energy level in TiO₂ is 0.62 eV high from the top of valence band, which belongs to the type of deep energy level doping. On the basis of the semiconductor energy level theory and Cr³⁺ dopant energy level, the semiconductor energy level model of Cr³⁺ in TiO₂ powder and thin film were established, and the doping mechanisms of Cr³⁺-doped in TiO₂ powder and thin film were analyzed. Foundation item: Project (20466001) supported by the National Natural Science Foundation of China