Dynamics of Electrochemical Noise of the Lithium Electrode in Aprotic Organic Electrolytes

Processes that occur on the lithium electrode under open-circuit conditions and when polarized cathodically and anodically are studied by means of the electrochemical-noise method. The study is carried out in such aprotic organic electrolytes as 1 M solution of LiClO₄ in 1,3-dioxolane; 1 M solution of LiPF₆ in a mixture of ethylene carbonate and diethyl carbonate; and 1 M solution of LiN(CF₃SO₂)₂ in 1,3-dioxolane. An analysis of the noise characteristics of the polarized electrode confirms that the electrochemical process is localized under the passivating film. Potential fluctuations of the electrode polarized at high current densities depend on the electrolyte nature. The amplitude of the electrochemical noise is maximum in the electrolyte system 1 M LiPF₆ in a mixture of ethylene carbonate and diethyl carbonate. The fluctuation intensity is found to correlate with the electrode stability when cycled. This fact suggests that the method can be used for express assessment of organic electrolytes intended for lithium batteries.     

约束凝固枝晶尖端扩散场的Zener近似因子

Ｚｅｎｅｒ近似因子是处理约束凝固枝晶尖端扩散场的重要参量．文章从尖端非平衡溶质分配的角度,给出了Ｚｅｎｅｒ近似因子λ的计算公式,指出λ是合金的物理性质及尖端推移速率和界面非平衡效应的综合反映;在此基础上,给出了各种稳态约束枝晶生长模型的适用速率范围,并与实验结果进行了比较．     

Steady needle growth with 3-D anisotropic surface tension

The effect of the anisotropic interfacial energy on dendritic growth has been an important subject, and has preoccupied many researchers in the field of materials science and condensed matter physics. The present paper is dedicated to the study of the effect of full 3-D anisotropic surface tension on the steady state solution of dendritic growth. We obtain the analytical form of the first order approximation solution in the regular asymptotic expansion around the Ivantsov’s needle growth solution, which extends the steady needle growth solution of the system with isotropic surface tension obtained by Xu and Yu (J. J. Xu and D. S. Yu, J. Cryst. Growth, 1998, 187: 314; J. J. Xu, Interfacial Wave Theory of Pattern Formation: Selection of Dendrite Growth and Viscous Fingering in a Hele-Shaw Flow, Berlin: Springer-Verlag, 1997). The solution is expanded in the general Laguerre series in any finite region around the needle-tip, and it is also expanded in a power series in the far field behind the tip. Both solutions are then numerically matched in the intermediate region. Based on this global valid solution, the dependence of Peclet number Pe and the interface’s morphology on the anisotropy parameter of surface tension as well as other physical parameters involved are determined. On the basis of this global valid solution, we explore the effect of the anisotropy parameter on the Peclet number of growth, as well as the morphology of the interface.      

球铁枝晶中硅锰元素偏析行为的研究

采用着色腐蚀法，借助电子探针定量分析了Ｓｉ、Ｍｎ元素在球铁枝晶中的分布特征及其偏析行为，以及碳当量、壁厚对Ｓｉ、Ｍｎ元素偏析行为的影响。结果表明：Ｓｉ在枝晶中的偏析系数ＫＳｉＳ和分配系数ＫＳｉ均大于１，而Ｍｎ的偏析系数ＫＭｎＳ和分配系数ＫＭｎ均小于１；Ｓｉ在奥氏体枝晶晶粒内分布具有一定的空间几何对称性，沿径向呈阶梯形分布特点；在Ｓｉ平均含量不变和试样壁厚相同的情况下，随着碳当量的增大，Ｓｉ、Ｍｎ元素在枝晶中的分配系数基本保持不变。     

Solute distribution in KNbO3 melt-solution and its effect on dendrite growth during rapid solidification

This paper reports that the rapid solidification of mixed Li 2 B 4 O 7 and KNbO 3 melted in a Pt loop heater has been performed experimentally by the method of quenching, and various morphologies of KNbO 3 crystals have been observed in different regions of the quenched melt-solution. Dendrites were formed in the central region where mass transfer is performed by diffusion, whereas polygonal crystals with smooth surface grew in the marginal region where convection dominates mass transport. Based on measurement of KNbO 3 concentration along crystal interface by electronic probe analysis, it finds the variety of crystal morphologies, which is the result of different solute distributions: in the central region the inhomogeneity of solute concentration is much sharper and morphological instability is easier to take place; nevertheless in the marginal region the concentration homogeneity has been greatly enhanced by convection which prevents the occurrence of morphological instability. Additional solute distribution in the melt along the primary dendrite trunk axis as well as that in mushy zones has also been determined. Results show that the solute concentration in the liquid increases linearly with distance from the trunk tip and more solutes were found to be concentrated in mushy zones. The closer the mushy zone is to trunk tip, the lower the solute concentration will be there.     

切向流动作用下SCN-3wt% H2O枝晶定向生长过程研究

实时观察了切向流动作用下SCN-3wt% H₂O合金的定向凝固过程,研究了该合金枝晶生长方向、尖端半径、枝晶一次臂间距以及二次臂生长速度的变化规律.实验观察到能够代表枝晶尖端溶质边界层的“亮带”,该亮带在流动作用下的非对称性证实了切向流动能够改变枝晶前沿溶质的对称分布,使溶质边界层厚度沿背流侧向迎流侧逐渐减薄,枝晶生长发生迎流偏转,且偏转角度随抽拉速度的提高而减小.同时,流场与浓度场的耦合促进枝晶间的优胜劣汰,枝晶一次臂间距显著增大.固液界面处的强迫流动还能够引发相邻枝晶间环流,加速迎流处二次臂生长而抑制背流处生长. 关键词： 定向凝固 枝晶生长 切向流动     

AuPd和AgPd枝晶纳米催化剂催化甲酸分解制氢

由枝晶构成的AuPd和AgPd三维多孔泡沫薄膜在室温下分解甲酸制氢具有高催化活性。该高催化活性是由于纳米枝晶中存在大量的活性位点,如台阶、角、扭结、边缘以及合金间的电子效应。多孔泡沫膜除了具有较高的活性外,还具有其他优良的性能：在不需要有机添加剂的情况下,利用氢气泡模板法在Ti基板上可在5 min内快速沉积多孔泡沫催化剂,无需后处理便可用于催化甲酸分解制氢;通过将电沉积泡沫膜浸入或者拉出HCOOH+HCOONa溶液,可控制氢气的产生或停止;该泡沫催化剂通过去离子水清洗或者在H₂SO₄溶液中进行循环伏安扫描、干燥后就可活化重新使用。     

Al-La合金不连续枝晶组织形成机理

在Al-La合金的自由凝固试样中,发现Al-35%La合金组织形貌的特殊性,其先结晶相Al11La3枝晶沿主干方向成分是不连续的. 为验证这种组织存在的真实性,采用定向凝固方法制备了不同冷却速度下的Al-35%La合金试样,结果显示出定向凝固Al-35%La合金中Al11La3枝晶沿主干方向成分是不连续的. 在此基础上,分析了化学成分与凝固速度对Al-La合金组织的影响,并初步探讨了这种不连续枝晶的形成机理.     

Settling velocity of equiaxed dendrites in a tube

The settling velocity of equiaxed dendrites can cause macrosegregation and influence the structure of the equiaxed zone during the casting solidification process. So an understanding of the settling characteristics is needed to predict the structure and segregation in castings. The settling velocity of NH4Cl equiaxed dendrites of non-spherical geometry was studied experimentally in an NH4Cl-70wt.%H2O solution. A calculation formula was proposed to calculate the settling velocity of sediment equiaxed dendrites in a tube filled with saturated solution at a moderate Reynolds number region. The retardation effects of the wall and morphology of the equiaxed dendrite on the settling velocity were taken into account in the development of the calculation formula, and the correction function B of the drag coefficient with consideration of the retardation effects of the wall and morphology of the equiaxed dendrite on the settling velocity of the equiaxed dendrite was calibrated according to the experimental results. A comparison showed that the formula has a good accordance with the experimental results.     

Forming solid electrolyte interphase in situ in an ionic conducting Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3-polypropylene(PP) based separator for Li-ion batteries

A new concept of forming solid electrolyte interphases(SEI) in situ in an ionic conducting Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3-polypropylene(LAGP-PP) based separator during charging and discharging is proposed and demonstrated. This unique structure shows a high ionic conductivity, low interface resistance with electrode, and can suppress the growth of lithium dendrite. The features of forming the SEI in situ are investigated by scanning electron microscopy(SEM) and x-ray photoelectron spectroscopy(XPS). The results confirm that SEI films mainly consist of lithium fluoride and carbonates with various alkyl contents. The cell assembled by using the LAGP-coated separator demonstrates a good cycling performance even at high charging rates, and the lithium dendrites were not observed on the lithium metal electrode. Therefore, the SEI-LAGP-PP separator can be used as a promising flexible solid electrolyte for solid state lithium batteries.