Li3Fe2(PO4)3/C正极材料的电化学性能及其反应机理研究

采用溶胶凝胶及高能球磨制得Li₃Fe₂(PO₄)₃/C材料,利用多种物理及其电化学技术观察材料形貌,表征材料结构及电化学性能,用电化学原位XAFS等初步研究Li₃Fe₂(PO₄)₃/C超理论容量电化学反应机理. 结果显示,Li₃Fe₂(PO₄)₃/C的结构为单斜晶系,空间群P21/n. 2.0 ~ 4.0 V电位区间,10 mAh·g^-1电流密度,Li₃Fe₂(PO₄)₃/C电极的首周期放电比容量为129 mAh·g^-1,达到其理论容量. 若电位区间拓宽至2.0 ~ 4.95 V,其首周期放电比容量高达165 mAh·g^-1,超出理论的“额外”容量30%. 电化学原位XAFS测试未观察到明显的Fe³⁺/Fe⁴⁺氧化还原对参与电化学反应,初步推测“额外”容量可能来自于该复合材料的高浓度表面缺陷.     

面向生物过程的阿达玛变换近红外光谱仪

对生物过程中营养物质的消耗进行监测,有利于控制微生物的生长环境,使其始终处于最佳生长条件,从而使目标产物的产量最大化。针对酵母培养液中甘油、甲醇和葡萄糖含量的监测需求,研制了一种基于阿达玛变换(hadamard transform,HT)技术的近红外光谱仪。该光谱仪使用自主改进设计的近红外原位探头进行光谱信号的收集,采用数字微镜(digital micro-mirror devices,DMD)进行阿达玛模板的编码调制,配合自主开发的光谱采集软件和光谱分析处理软件,实现了培养液中营养物含量的实时监测。给出了光谱仪的光路设计、近红外原位探头改进设计、硬件电路和软件模块的设计。通过实验测得该光谱仪的杂散光为0.875%,波动率为±4.28%。利用该光谱仪对一系列标准浓度的甘油水溶液进行光谱采集和数学建模,实验结果表明该仪器测量准确,能够满足生物过程监测的要求。     

Fluid Flow Across Capillary Heterogeneities,Experiments and Simulations

A comparative study of numerical modelling and laboratory experiments of two-phase immiscible displacements in a 33 cm × 10 × 3 cm thick cross-bedded reservoir model is reported. Dynamic two-dimensional fluid saturation development was obtained from experiments by use of a nuclear tracer imaging technique and compared to numerical predictions using a full-field black oil simulator.The laboratory cross-bedded reservoir model was a sandpack consisting of two strongly waterwet sands of different grain sizes, packed in sequential layers. The inlet and outlet sand consisted of low permeable, high capillary, sand while the central crosslayer with a dip angle of 30° was a high permeable, low capillary, sand. Results on moderate contrasts in permeability and capillary heterogeneities in the cross-bedded reservoir model at different mobility ratios and capillary number floods temporarily showed a bypass of oil, resulting in a prolonged two-phase production. The final remaining oil saturations, however, were as for isolated samples. Hence, permanently trapped oil was not observed.Simulations of waterfloods, using a commercial software package, displayed correct water breakthrough at low flow rate and unity viscosity ratio, but failed in predicting local saturation development in detail, probably due to numerical diffusion.The simulator was used to test several cases of heterogeneity contrasts, and influence from different relative permeability curves. Further, by altering the capillary pressure at the outlet, the end effects were proven important.     

The attenuation of oscillatory thermocapillary convection in the oxide melt by a transverse magnetic field

The effect of a transverse magnetic field on the oscillatory thermocapillary convection in the NaBi(WO4)2 melt was studied by using the in-situ observation system. The oscillation was attenuated when the 60 mT magnetic field was applied, as shown by the decrease in the amplitude and the frequency. Furthermore, the oscillation under smaller temperature difference was stabilized after the magnetic field was applied. The magnetic effect could be due to the Lorentz force generated by the interaction between motional ions and the vertical magnetic field. The ionic conductivities were measured to demonstrate the effect of the magnetic field. The solid ionic electrical conductivity increases with the temperature rise, and the melt ionic electrical conductivity was measured to be about 2.0×10-4 Ω-1·cm-1. Experimental results manifest that the effect of the magnetic field on anions and cations in the melt makes the flow change to the direction normal to the applied field, so the flow is more orderly and the oscillation is suppressed.     

Tuning the Redox Chemistry of a Cr/SiO2 Phillips Catalyst for Controlling Activity,Induction Period and Polymer Properties

The Cr/SiO₂ Phillips catalyst has taken a central role in ethylene polymerization ever since its discovery in 1953. This catalyst is unique compared to other ethylene polymerization catalysts, since it is active without the addition of a metal-alkyl co-catalyst. However, metal-alkyls can be added for scavenging poisons, enhancing the catalyst activity, reducing the induction period and altering polymer characteristics. Despite extensive research into the working state of the catalyst, still no consensus has been reached. Here, we show that by varying the type of metal-alkyl co-catalyst and its amount, the Cr redox chemistry can be tailored, resulting in distinct catalyst activities, induction periods, and polymer characteristics. We have used in-situ UV-Vis-NIR diffuse reflectance spectroscopy (DRS) for studying the Cr oxidation state during the reduction by tri-ethyl borane (TEB) or tri-ethyl aluminum (TEAl) and during subsequent ethylene polymerization. The results show that TEB primarily acts as a reductant and reduces Cr⁶⁺ with subsequent ethylene polymerization resulting in rapid polyethylene formation. TEAl generated two types of Cr²⁺ sites, inaccessible Cr³⁺ sites and active Cr⁴⁺ sites. Subsequent addition of ethylene also revealed an increased reducibility of residual Cr⁶⁺ sites and resulted in rapid polyethylene formation. Our results demonstrate the possibility of controlling the reduction chemistry by adding the proper amount and type of metal-alkyl for obtaining desired catalyst activities and tailored polyethylene characteristics.     

金属-有机骨架[Zn(BDC)(H2O)2]n膜的原位制备及其对硝基苯类有机物的可逆检测

采用水热法,将锌片与对苯二甲酸(H2BDC)反应原位合成[Zn(BDC)(H2O)2]n薄膜.利用XRD和SEM分别对薄膜的结构、形貌和尺寸等进行了表征.结果表明,薄膜是由一维链状结构的金属-有机骨架材料纳米晶构成的,随着水热时间的增加,薄膜中的[Zn(BDC)(H2O)3]n纳米晶晶粒尺寸逐渐减小.该薄膜在紫外光的激...     

Determination of ultra-trace amounts of nickel in environmental samples by atomic absorption spectrometry with in-situ trapping of volatile species in an iridium–palladium coated graphite furnace

A sensitive and accurate method is described for the determination of ultra-trace nickel in environmental samples with in-situ trapping of volatile species in iridium-palladium coated graphite furnace atomic absorption spectrometry. The effects of the conditions for the generation and collection of volatile nickel species, such as medium acidity, potassium borohydride concentration, enhancement reagent concentration, reaction temperature, as well as graphite tube coating, carrier gas flow rate and trapping time were investigated. Phenanthroline was selected as the enhancement reagent due to its good enhancing effect, and iridium–palladium coating was used for the in-situ trapping of volatile nickel species at 300°C. Under the optimal conditions, the calibration curve was linear from 0.21 up to 30.0 ng mL^?1 with correlation coefficient of 0.9991, the detection limit (S/N = 3) was 0.21 ng mL^?1 for 4 mL sample volumes and the relative standard deviation for 11 determinations of Ni at 10 ng mL^?1 was 3.5%. The results found by the proposed methods are accordant with the certified values of water, soil and tea certified reference materials. The proposed methods have been applied for the determination of ultra-trace Ni in tap, river and wastewater, as well as rice and soil samples, with recoveries ranging from 97.3 to 100.5%.     

电化学过程原位质谱分析研究进展

质谱分析法以其灵敏度高、特异性强、分析通量高等特点,近年来已逐步用于电化学反应过程的原位监测和机理探究.通过开发新型电离源以及构建电化学池-质谱偶联装置,研究者们相继发展了一系列电化学质谱(EC-MS)分析方法,并在电化学过程产物实时监测、同位素标记分析、短寿命中间体捕获鉴定等方面展现出了特有的技术优势.该综述从气相及...     

原位复合法制备(PEO)8LiClO4/TiO2聚合物电解质的研究

以聚氧化乙烯/高氯酸锂复合物[(PEO)8LiClO4]为基体,通过钛酸丁酯的水解缩合反应在其中原位生成TiO2,制备了(PEO)8LiClO4/TiO2复合聚合物电解质,采用SEM、DSC和交流阻抗方法研究了聚合物电解质的形态、玻璃化转变温度(Tg)、结晶度(Xc)和离子导电性能.结果表明原位生成的TiO2在基体中分散均匀,加入TiO2后聚合物电解质体系的Tg和Xc均有所降低,而电导率明显提高,当TiO2添加量为ω=0.05时电导率达到最大值5.5×10-5S·cm-1(20℃).     

基于超精密机床的光学自由曲面原位测量方法

原位测量是提高光学自由曲面面形精度的重要手段,对于提高加工效率、实现加工过程自动化具有重要意义。由于面形的复杂性,光学自由曲面原位测量一直是超精密测量领域的难题。提出了一种基于超精密机床的光学自由曲面原位测量方法,测量系统由LVDT气浮式传感器、红宝石探针和数据采集部件组成,采用螺旋线方式进行加工及测量路径的设计,通过运动控制接口实现机床坐标和测量数据的实时同步采集,快速精确地获取测量数据。实验结果表明,所加工的双正弦自由曲面的面形误差在±0.5μm范围内。