The Markov chain model of alloy electrodeposition: application to NiCo and NiMo

The Markov chain model of alloy deposition was applied to cobalt–nickel. The characteristic parameters of the model are the g _i values describing the selectivity of the deposition process for its components. The values recently determined for Co and Ni (g _Co and g _Ni) depend on the current density. This could be quantitatively described by the mass transport limitation for Co. The model was also applied to the nickel–molybdenum system, an example for induced co-deposition. Data published by Podlaha and Landolt [4, 5] could be described by the equation

Combined transformations of carbon dioxide and ethanol in the presence of the intermetallic compound TiFe0.95Zr0.03Mo0.02, Pd/SiO2, and Al2O3

The influence of the composition of catalytic systems and the method for H₂ feed into the reaction area on the degree of conversion of CO₂ during its joint transformations with ethanol and on the selectivity of formation of liquid organic products (ethyl acetate, acetaldehyde, and hydrocarbons) was studied atp=15 atm andT=573 K. A noticeable conversion of CO₂ and ethanol into ethyl acetate and acetaldehyde was observed in the presence of only the intermetallic compound, its composition with a palladium-containing catalyst, and the whole ternary catalytic system. The selectivity of the reaction changed when the binary catalytic composition consisting of the intermetallic and γ-Al₂O₃ was used. In this case, the fraction of C₉–C₁₄ alkenes and alkenes with normal and iso structures was mostly formed; its content was as high as 40%. The degree of conversion of CO₂ reached 30–36% and the selectivity to liquid products was 70–80% only when the hydrogen desorbed from the intermetallic was used. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1360–1364, July, 1998.     

Electrochemical deposition: the concept of residence times in structure development

The concept of the residence time of an atom in a kink position was introduced to predict the structure of electrochemically deposited surface coatings. The residence time is obtained from the reciprocal value of the rate constant for separation from the kink position. Residence times and deposition rates determine the density of kink positions [ksp] on the growing metal film. For equilibrium conditions (Nernst potential), the density of kink positions [ksp]₀ depends on the exchange current density i₀ and on the residence time by the equation:

Sodium and silver phosphate glasses doped with chlorides of Fe,Mn and Zn

A number of samples of sodium and silver phosphate glasses doped with various compositions of some transition metals viz. iron, manganese and zinc chlorides alongwith undoped samples of sodium and silver phosphate glasses were synthesized and characterized by X-ray diffraction, IR spectral, electrical conductivity and differential scanning calorimetry (DSC). The glass transition temperature (T _g) and crystallization temperature (T _c) values obtained from DSC curves were found to increase with increasing concentration of the dopant Fe/Mn/Zn chlorides in both sodium and silver phosphate glasses and the following sequence is observed: T _g(–FeCl₃)>T _g(–MnCl₂)>T _g(–ZnCl₂) T _c(–FeCl₃)>T _c(–MnCl₂)>T _c(–ZnCl₂) The increase in T _g and T _c values indicate enhanced chemical durability of the doped glasses. The electrical conductivity values and the results of FTIR spectral studies have been correlated with the structural changes in the glass matrix by the addition of different transition metal cations as dopants.     

Electrochemical properties of LiFePO4/C synthesized using polypyrrole as carbon source

LiFePO₄/C composites were synthesized by pyrolysis of LiFePO₄/polypyrrole (PPy), which was obtained by an in situ chemical polymerization involving pyrrole monomer and hydrothermal synthesis LiFePO₄. All samples were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, cyclic voltammetry, and galvanostatic charge–discharge techniques. The results showed the LiFePO₄/C sintered at 800 °C containing 2.8 wt.% carbon exhibited a higher discharge capacity of 49.6 mAh·g⁻¹ at 0.1 C, and bare LiFePO₄ only delivered 11.6 mAh·g⁻¹ in 2 M LiNO₃ aqueous electrolyte. The possible reason for the improvement of electrochemical performance was discussed and could be attributed to the formation of aromatic compounds during the carbonization of PPy.     

NiO/MnO_2分级纳米片阵列复合材料的制备与超电容性能

通过化学浴沉积和水热法在泡沫镍上制备了NiO/MnO_2分级纳米片阵列复合材料,XRD和SEM测试表明NiO纳米片垂直生长在泡沫镍上,交叉形成网状阵列结构;MnO_2纳米介孔泡沫进一步生长在NiO纳米片两侧,与NiO形成了壳核式的复合结构。循环伏安和恒流充放电测试发现,NiO/MnO_2分级纳米片阵列复合材料的电化学性能相比复合前得到明显改善,在1 A·g~(-1)的电流密度下,比电容提高至1 297 F·g~(-1);2 A·g~(-1)下循环1 000次,比电容保持率高达97%,比电容和循环性能的改善是由于分级纳米片阵列复合结构方便了电解液传质,扩大了活性材料与电解液的接触,促进了赝电容反应,提高了NiO和MnO_2的结构稳定性。     

NiO/MnO2分级纳米片阵列复合材料的制备与超电容性能

通过化学浴沉积和水热法在泡沫镍上制备了NiO/MnO₂分级纳米片阵列复合材料,XRD和SEM测试表明NiO纳米片垂直生长在泡沫镍上,交叉形成网状阵列结构;MnO₂纳米介孔泡沫进一步生长在NiO纳米片两侧,与NiO形成了壳核式的复合结构。循环伏安和恒流充放电测试发现,NiO/MnO₂分级纳米片阵列复合材料的电化学性能相比复合前得到明显改善,在1 A·g^-1的电流密度下,比电容提高至1 297 F·g^-1;2 A·g^-1下循环1 000次,比电容保持率高达97%,比电容和循环性能的改善是由于分级纳米片阵列复合结构方便了电解液传质,扩大了活性材料与电解液的接触,促进了赝电容反应,提高了NiO和MnO₂的结构稳定性。     

Facile preparation and electrochemical properties of large-scale Li<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript>3</Subscript>O<Subscript>8</Subscript> nanobelts

Large-scale Li_1+x V₃O₈ nanobelts were successfully fabricated using filter paper as deposition substrate through a simple surface sol–gel method. The nanobelts were as long as tens of micrometers with widths of 0.4–1.0 μm and thickness of 50–100 nm. The nanobelts were characterized by X-ray diffration (XRD), Fourier infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM). The formation mechanism of the nanobelts was investigated, showing that the morphology of the nanobelts is mainly determined by the calcination temperature. Electrochemical properties of the Li_1+x V₃O₈ nanobelts were characterized by charge–discharge experiments, and the results demonstrate that the Li_1+x V₃O₈ nanobelts exhibit a high discharge capacity (278 mAh g⁻¹) and excellent cycling stability.     

σ-Alkynylcopper(i) and σ-alkynylpalladium(ii) complexes as intermediates in catalytic oxidative carbonylation of alkynes to alkynoates

Hypothetical mechanisms of oxidative carbonylation of alkynes to alkynoates in the PdCl₂-CuCl₂-base system are discusssed. σ-Alkynylcopper(i) and σ-alkynylpalladium(ii) complexes are considered to be the most probable intermediates in the process. A kinetic model of the reaction is proposed. The oxidative carbonylation of RC≡CCu in the PdCl₂-CuCl₂-base system leads to the formation of RC≡CCOOR'. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1806–1809, October, 1993.     

稀土元素对R-Y-Ni系A2B7型无镁储氢合金微观结构和电化学性能的影响

采用真空电弧熔炼及退火处理制备R-Y-Ni系A_2B_7型R0.3Y0.7Ni3.25Mn0.15Al0.1(R=Y,La,Pr,Ce,Nd,Gd,Sm)储氢合金,系统研究稀土元素R对合金微观组织与结构、储氢和电化学性能的影响。XRD和SEM-EDS分析表明,合金退火组织由Ce2Ni7型主相、PuNi3型及少量Ca Cu5型相组成,Ce2Ni7型主相的晶格常数a、c及晶胞体积V均随稀土R原子半径的减小而依次降低。该合金均具有明显的吸放氢平台,常温下最大吸氢容量为1.17%~1.48%(w/w),吸氢平台压Peq为0.037~0.194 MPa。电化学分析表明,退火合金电极的电化学活化性能优良,R=La合金具有最高的放电容量(389.2 mAh·g-1)和较佳的容量保持率(充放电循环100次后的S100=85.7%),其中合金微观组织的不均匀性及稀土元素的电化学腐蚀是影响电极循环稳定性的主要原因。合金电极的高倍率放电性能(电流密度为900 m A·g-1)HRD900=71.05%~86.94%,其电极反应动力学控制步骤主要由氢原子在合金体相中的扩散速率所控制。     

Mn4+掺杂Co3O4纳米纤维的静电纺丝法制备及其电化学性能

通过静电纺丝法制备Mn~(4+)掺杂的Co_3O_4复合纳米纤维,利用XRD、XPS、BET、SEM和电化学工作站等对材料的结构、成分、形貌和电化学性能进行表征与测试。研究发现,通过Mn~(4+)掺杂,Co_3O_4复合纳米纤维的电化学性能得到明显改善。当nCo∶nMn=20∶2时,相应的复合纤维具有较大比表面积68 m2·g-1,而且该样品呈现出清晰的氧化还原峰,在1 A·g-1的电流密度下,放电比电容量为585 F·g-1,这比纯Co_3O_4纳米纤维的416 F·g-1,有显著提高;循环500圈电容保持率达到82.6%,而纯Co_3O_4纳米纤维则是76.4%。     

Dynamic analysis on metal selenide electrodeposition

Based on the basic principles of kinetics and some reasonable assumptions about the electrodeposition process, a dynamic model for metal selenide electrodeposition (kink site selected model) was constructed. This model is of universal significance in realizing the compositional prediction and dynamic behavior analysis of deposited films for different main salt concentration ratios and was applied to the ternary Cu–In–Se system. For CuInSe₂ electrodeposition, in the Cu–Se system, the co-deposition of Cu and Se can be carried out within a large range of main salt concentration ratio; in the Cu–In system, the mole fraction of Cu in deposited thin films is always higher than that of Cu²⁺ in electrolyte, while in the In–Se system, the co-deposition of In and Se can be achieved only when the In³⁺ concentration is much higher than the H₂SeO₃ concentration. As for the compositional estimation of CuInSe₂, the predictive results of our dynamic model agree well with the experimental data. It is then found that by correcting the difference of kink site selectivity constants caused by the change of deposition potential, the error of the predictive results can be reduced.     

Ti3C2Tx/MnO2正极在水系锌电池中的电化学性能

二氧化锰(MnO₂)材料具有比容量大、电极电位高、储量丰富以及价格低廉等优势,成为水系锌电池正极最受关注的一类材料,然而其仍然存在着结构稳定性差和电化学储存机理复杂的问题。因此,我们通过两步合成法制备了一种花苞状结构的MnO₂负载在Ti₃C₂T_x表面形成Ti₃C₂T_x/MnO₂复合材料,通过X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)对复合样品的结构、成分和形貌进行表征。通过将Ti₃C₂T_x/MnO₂复合材料作为正极,与锌负极匹配组装成水系锌电池,研究了其分别在2 mol·L^-1 ZnSO₄、2 mol·L^-1 ZnSO₄+0.1 mol·L^-1 MnSO₄、30 mol·L^-1三氟甲基磺酸四乙基铵(TEAOTf)+1 mol·L^-1三氟甲烷磺酸锌(ZnOTf)和3 mol·L^-1 ZnOTf四种电解液中的电化学性能。结果表明,Ti₃C₂T_x/MnO₂在2 mol·L^-1 ZnSO₄中的比容量较高,但循环稳定性很差。将TEAOTf盐和ZnOTf盐共溶于水中,设计了一种新型的含惰性阳离子的超高浓度盐包水电解液(30 mol·L^-1 TEAOTf+1 mol·L^-1 ZnOTf),不仅提高了Ti₃C₂T_x/MnO₂材料的可逆性,而且有效抑制了电极材料在循环过程中的溶解。     

Study of the selectivity of a V2O5?ZrO2 catalyst for partial oxidation ofo-xylene at high temperatures

It has been established that at high temperatures (above 450°C) the V₂O₅−ZrO₂ catalyst exhibits a higher selectivity in the oxidation ofo-xylene to phthalic anhydride than does the conventional V₂O₅−TiO₂(a) catalyst. The catalyst selectivity is found to increase with respect to partial oxidation ofo-xylene, the valuable by-product maleic anhydride being obtained. Studies by different physicochemical methods have shown that V₂O₅−ZrO₂ undergoes no significant phase and structural changes under high-temperature conditions.     

Mn4+掺杂Co3O4纳米纤维的静电纺丝法制备及其电化学性能

通过静电纺丝法制备Mn⁴⁺掺杂的Co₃O₄复合纳米纤维,利用XRD、XPS、BET、SEM和电化学工作站等对材料的结构、成分、形貌和电化学性能进行表征与测试。研究发现,通过Mn⁴⁺掺杂,Co₃O₄复合纳米纤维的电化学性能得到明显改善。当n_Co∶n_Mn=20∶2时,相应的复合纤维具有较大比表面积68 m²·g^-1,而且该样品呈现出清晰的氧化还原峰,在1 A·g^-1的电流密度下,放电比电容量为585 F·g^-1,这比纯Co₃O₄纳米纤维的416 F·g^-1,有显著提高;循环500圈电容保持率达到82.6%,而纯Co₃O₄纳米纤维则是76.4%。     

Atomic distributions in liquid copper-tin alloys

Abstract

Molten copper-tin alloys have been studied by X-ray diffraction, using a focusing theta-theta diffraetometer and Mo-Kα radiation (monochromator in the diffracted beam). Five alloys with 20, 35, 45, 55 and 78 atomic percent Sn, and pure Cu and Sn were measured at temperatures about 20 °C above the liquidus, and at 1100 °C. The total interference functions I(K), where K = 4π sin θ/δ, were obtained from the observed scattered intensities I_a(K) per atom and the theoretical atomic scattering factors. Splitting of the first peak in I(K) has been observed in the Cu-55 at% Sn alloy at the liquidus temperature.

The partial interference functions I_tj(K) at the liquidus temperature and at 1100°C were evaluated (assuming that they are independent of atomic concentration) using the five total I(K) of the alloys. The functions I_ij(K) are in reasonable agreement with those obtained by Enderby, North and Egelstaff from neutron diffraction data of a Cu-45 at % Sn alloy.

The reduced partial distribution functions G_ij(r) = 4πρ₀ r{g_ij(r) ? 1} and the probability functions g_ij(r) = ρ _ij(r)/c_j ρ₀, where ρ _ij(r) is the number of j-type atoms per unit volume at the distance r from an i-type atom, c_j is the atomic fraction of j-type atoms and ρ₀ is the average atomic density, have been evaluated by Fourier transformation of {I_ij(K) ? 1} K.

The electrical resistivities ρ _R of the alloys, calculated with the Faber-Ziman equation using the measured I_ij(K) and Animalu-Heine pseudo-potential elements U_i(K), are in good agreement with the experimental values of Roll and Motz. Assuming that U_i (2k _F) is independent of the values of the Fermi diameter 2k _F of the alloys, the concentration dependence of (3 - X)ρR, where X is the thermoelectric parameter measured by Enderby and Howe, is well reproduced when using the X-ray values of I_ij (2k _F).     

Preparation and characterization of nanotube Li-Ti-O by molten salt method

Nanotube Li-Ti-O compound with high surface (198.6 m²·g⁻¹) was prepared by a method involving the treatment of nanotube Na₂Ti₂O₅·H₂O in molten LiNO₃ and characterization by means of transmission electron microscopy (TEM), energy-dispersive spectra (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and thermogravimetry-differential thermal analysis (TG/DTG). Results show that the nanotube Li-Ti-O compound prepared by this method involves two crystal phases: spinel Li₂Ti₂O₄ and anatase Li_xTiO₂ (x < 0.1). Li⁺ exhibits different Li1s binding energy in the two crystal phases. In ambient air, the Li-Ti-O compound adsorbs water easily, and the chemically adsorbed water is difficult to remove below 400°C. Translated from Chinese Journal of Inorganic Chemistry, 2006, 22(12): 2135–2139 [译自: 无机化学学报]     

Effect of TiO2-coating on structure and electrochemical performance of LiCo0.2Ni0.4Mn0.4O2

LiCo_0.2Ni_0.4Mn_0.4O₂, as the cathode material for lithium ion batteries, was modified by TiO₂-coating. The effect of TiO₂-coating on the structure and electrochemical performance of LiCo_0.2Ni_0.4Mn_0.4O₂ was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and galvanostatic charge-discharge tests. The results suggest that a small amount of TiO₂-coating does not change the crystalline structure, but considerably improves the electrochemical performance of LiCo_0.2Ni_0.4Mn_0.4O₂ in terms of capacity delivery and cyclability. XPS measurements confirm that the improved electrochemical performance is most possibly attributed to a decrease in interaction between the layered material and non-aqueous electrolyte during the charge-discharge processes. __________ Translated from Chinese Journal of Inorganic Chemistry, 2007, 23(5): 753–758 [译自: 无机化学学报]     

二维层状Ti3C2Tx-MXene@VS2用于高性能锂离子电池负极

为探索一种高性能的锂离子电池负极材料,采用酸刻蚀法制备了高导电性、高稳定性的二维层状Ti₃C₂T_x,通过溶剂热法制备了具有高理论比容量的花瓣状VS₂纳米片,再经过简单的液相混合得到了二维层状Ti₃C₂T_x-MXene@VS₂复合物。通过扫描电子显微镜、透射电子显微镜、X射线光电子能谱、X射线衍射和能谱分析对复合材料的形貌和结构进行了表征,采用循环伏安、恒流充放电、长循环和交流阻抗谱对复合材料的电化学性能进行了研究。结果表明：VS₂纳米片均匀地分布在Ti₃C₂T_x的层间及表面,该复合物具有高的可逆容量(电流密度为0.1A·g^-1时,比容量为610.5mAh·g^-1)、良好的倍率性能(电流密度为2A·g^-1时,比容量为197.1mAh·g^-1)和良好的循环稳定性(电流密度为0.2 A·g^-1时,循环600圈后比容量为874.9 mAh·g^-1;电流密度为2 A·g^-1时,循环1 500圈后比容量为115.9mAh·g^-1)。     

Synthesis and electrochemical properties of nanostructured LiAl x Mn2 − x O4 − y Br y particles

Nanostructured LiAl _x Mn_2 − x O_4 − y Br _y particles were synthesized successfully by annealing the mixed precursors, which were prepared by room-temperature solid-state coordination method using lithium acetate, manganese acetate, lithium bromide, aluminum nitrate, citric acid, and polyethylene glycol 400 as starting materials. X-ray diffractometer patterns indicated that the particles of the as-synthesized samples are well-crystallized pure spinel phase. Transmission electron microscopy images showed that the LiAl _x Mn_2 − x O_4 − y Br _y samples consist of small-sized nanoparticles. The results of galvanostatic cycling tests revealed that the initial discharge capacity of LiAl_0.05Mn_1.95O_3.95Br_0.05 is 119 mAh g⁻¹; after the 100th cycle, its discharge capacity still remains at 92 mAh g⁻¹. The introduction of Al and Br in LiMn₂O₄ bring a synergetic effect and is quite effective in increasing the capacity and elevating cycling performance.