Dense Sphene-type Solid Electrolyte Through Rapid Sintering for Solid-state Lithium Metal Battery

The sphene-type solid electrolyte with high ionic conductivity has been designed for solid-state lithium metal battery. However, the practical applications of solid electrolytes are still suffered by the low relative density and long sintering time of tens of hours with large energy consumption. Here, we introduced the spark plasma sintering technology for fabricating the sphene-type Li_1.125Ta_0.875Zr_0.125SiO₅ solid electrolyte. The dense electrolyte pellet with high relative density of ca. 97.4% and ionic conductivity of ca. 1.44×10^-5 S/cm at 30℃ can be obtained by spark plasma sintering process within the extremely short time of only ca. 0.1 h. Also the solid electrolyte provides stable electrochemical window of ca. 6.0 V(vs. Li⁺/Li) and high electrochemical interface stability toward Li metal anode. With the enhanced interfacial contacts between electrodes and electrolyte pellet by the in-situ formed polymer electrolyte, the solid-state lithium metal battery with LiFePO₄ cathode can deliver the initial discharge capacity of ca. 154 mA·h/g at 0.1 C and the reversible capacity of ca. 132 mA·h/g after 70 cycles with high Coulombic efficiency of 99.5% at 55℃. Therefore, this study demonstrates a rapid and energy efficient sintering strategy for fabricating the solid electrolyte with dense structure and high ionic conductivity that can be practically applied in solid-state lithium metal batteries with high energy densities and safeties.     

色谱灰色数模的建立及其应用研究(Ⅰ)──连续GM(1,N)模型的建立及色谱保留行为的预测

应用灰色系统理论和最小二乘原理，推导出连续GM（1，N）模型，并将该模型用于高效液相色谱中溶质保留行为的预测．研究了烷烃、烷基苯及对羟基苯甲酸酯等化合物的容量因子与流动相组成、容量因子与碳数、保留时间与温度、保留时间与碳数的关系，并建立了相应的数学模型，经验证，预测结果良好．     

铱(III)离子催化铈(IV)离子氧化四氢糠醇的动力学及机理

在酸性介质中用氧化还原滴定法研究了铈(IV)离子在痕量铱(III)离子催化作用下，于298~313 K区间氧化四氢糠醇(THFA)的反应动力学. 结果表明，反应对铈(IV)离子为一级，对铱(III)离子也为一级，对四氢糠醇的表观反应级数为正分数. 准一级速率常数kobs随[H+]增加而增大，而随[HSO₄－]增加而减小. 在氮气保护下，反应能引发丙烯腈聚合，说明在反应中有自由基产生. 通过kobs与[HSO₄－]的依赖关系，找到本反应体系的动力学活性物种是Ce(SO₄)₂，并计算出平衡常数，速控步骤的速率常数及相应的活化参数.     

新试剂N-苯基-N′-(氨基对苯磺酸钠)硫脲的合成及其在微量金(Ⅲ)测定中的应用

介绍了新试剂N 苯基 N′ (氨基对苯磺酸钠 )硫脲 (PPT)的合成方法。并研究了与金的显色条件 ,建立了光度法测定微量金的新方法。在pH 5 .0～ 5 8的HAc NaAc缓冲体系中 ,在溴化十六烷基三甲胺 (CTMAB)存在下 ,Au(Ⅲ )与PPT形成组成比 1∶3的黄色水溶性络合物 ,其最大吸收峰位于 31 7.0nm ,表观摩尔吸光系数ε=3.68× 1 0 4 L/mol·cm ,Au(Ⅲ )含量在 0～ 80 μg/2 5mL范围内服从比尔定律。     

纳米/微米碳酸钙的结构表征和热分解行为

采用棕榈酸对纳米碳酸钙进行有机表面改性, 运用SEM﹑TEM、XRD、FTIR 及TG-DTG 对表面改性前后的纳米碳酸钙进行表征, 并与微米碳酸钙的微晶结构及热分解特性进行比较. FTIR 分析结果确证了棕榈酸与纳米碳酸钙表面是以化学键合和物理吸附方式相结合, 粒子表面存在羧基等有机官能团的红外吸收特征. 对比研究发现, 碳酸钙微晶纳米化后, 其红外V3特征吸收峰出现约35 cm-1 的蓝移现象, 并且明显窄化. 初步解释了纳米碳酸钙红外吸收峰蓝移的原因, 认为尺寸效应和晶体场效应是影响纳米碳酸钙红外光谱特征的主要因素. 微晶结构的变化使得纳米碳酸钙的热分解反应表现出反常特性, 热分解温度较微米碳酸钙下降了40.6 ℃.     

铈离子与氨基甲酸酯类化合物引发丙烯酰胺聚合的研究

本文对铈离子与苯基氨基甲酸酯类化合物在H_2O-CH_3CN(3∶1,V/V)及H_2O-HCONH_2(1∶2,V/V)两种介质中引发丙烯酰胺的聚合进行了研究。考察了不同结构的苯基氨基甲酸酯对聚合的影响。苯基氨基甲酸酯类化合物对铈离子引发聚合均有促进作用,其中对-甲苯基氨基甲酸酯的促进作用最为显著。测定了聚合反应表现活化能及聚合动力学方程,并提出了聚合反应机理。     

Electric conductivity in a fibrous porous medium with thin but polarized double layers

The electric conduction in the fibrous medium constructed by a homogeneous array of parallel, identical, charged, circular cylinders having an arbitrary zeta potential filled with the solution of a symmetrically charged electrolyte is analytically examined. The thickness of the electric double layers surrounding the dielectric cylinders is assumed to be small relative to the radius of each cylinder and to the gap width between two neighboring cylinders, but the polarization of the mobile ions in the diffuse layers is allowed. The effect of interactions among individual cylinders is taken into explicit account by employing a unit cell model. The appropriate equations of conservation of electrochemical potential energies of ionic species are solved for each cell, in which a cylinder is envisaged to be surrounded by a coaxial cylindrical shell of the fluid solution. Analytical expressions for the effective electric conductivity are obtained in closed forms as functions of the porosity of the fiber matrix and other characteristics of the porous system. Comparisons of the results of the cell model with different conditions at the outer boundary of the cell are made. Under an otherwise identical condition, the electric conductivity in a porous medium composed of an array of parallel cylinders in the transverse direction is smaller than that of a suspension of spheres. The effect of interactions among the cylinders or spheres on the effective conductivity can be quite significant under appropriate conditions.     

Synthesis and Crystal Structure of 3,3‘—（Hexane—1,6—diyl）bis（1—acetyl—5,5—dimethylhydantoin）,a New Inducer of Differentiation

The title compound C20H30N4O6, Mr = 422.48)was synthesized and its crystal structure was determined by X-ray diffraction method. It crystallizes in the triclinic system, space group P ī with cell parameters: a = 8.330(2), b = 8.468(2), c = 16.017(3) A, α = 97.30(3), β = 92.33(3), γ = 103.94(3)o, V = 1084.7(4) A3, Dc = 1.294 g/cm3, Z = 2, F(000) = 452 and μ = 0.096 mm-1. The structure was refined to R = 0.0483 for 3732 observed reflections with I>2(I) and wR = 0.1335 for 4828 unique reflections. The hydantoin rings are planar and the two ring planes of one molecule are paralleled to each other.     

Particle interactions in electrophoresis: I. Motion of two spheres along their line of centers

The electrophoretic motion of two charged colloidal spheres with very thin electrical double layers in a constant applied electric field along their line of centers is considered. The particles may differ in radius and in zeta potential at the surface. The electrostatic and hydrodynamic governing equations are solved in the quasi-steady situation using bipolar coordinates and the electrophoretic velocities of particles are calculated for various cases. The interaction effect between particles can be very significant when the distance between particle surfaces gets close to zero. The particle with smaller zeta potential is speeded up by the motion of the other, which is retarded at the same time by the motion of the former one, if the two spheres have unequal zeta potentials of the same electrical sign. For two particles of different signs in zeta potential, motions of both are hindered by each other. The influence of the interaction between particles in general is stronger on the smaller one than on the larger one. For the special case of two electrophoretic spheres with identical zeta potentials, there is no particle interaction for all particle sizes and separations.     

Synthesis of poly(<Emphasis Type="Italic">N</Emphasis>-methylolacrylamide)/polymethylacrylamide hybrids via frontal free-radical polymerization

In this study, poly(N-methylolacrylamide)/polymethylacrylamide (PNMA/PMAA) hybrids were produced successfully by frontal free-radical polymerization at ambient pressure. In a typical run, the appropriate amounts of reactants (N-methylolacrylamide, NMA; methylacrylamide, MAA) and initiator (ammonium persulfate) were dissolved in dimethyl sulfoxide at ambient temperature. Frontal polymerization (FP) was initiated by heating the wall of the tube with a soldering iron, and the resultant hot fronts were allowed to self-propagate throughout the reaction vessel. Once initiated, no further energy was required for polymerization to occur. The dependences of the front velocity and front temperature on the initiator concentration, reactant dilution, and NMA/MAA components were thoroughly investigated. The front temperatures were between 69 and 116 °C, depending on the persulfate concentration. We have also investigated the FP of PNMA/PMAA hybrids with N-methyl-2-pyrrolidone as solvent. Results show that FP can be exploited as a means for the preparation of PNMA/PMAA hybrids with the potential advantage of higher throughput compared to the traditional mode.