Colloidal Supercapattery: Redox Ions in Electrode and Electrolyte

Redox chemistry is the cornerstone of various electrochemical energy conversion and storage systems, associated with ion diffusion process. To actualize both high energy and power density in energy storage devices, both multiple electron transfer reaction and fast ion diffusion occurred in one electrode material are prerequisite. The existence forms of redox ions can lead to different electrochemical thermodynamic and kinetic properties. Here, we introduce novel colloid system, which includes multiple varying ion forms, multi‐interaction and abundant redox active sites. Unlike redox cations in solution and crystal materials, colloid system has specific reactivity‐structure relationship. In the colloidal ionic electrode, the occurrence of multiple‐electron redox reactions and fast ion diffusion leaded to ultrahigh specific capacitance and fast charge rate. The colloidal ionic supercapattery coupled with redox electrolyte provides a new potential technique for the comprehensive use of redox ions including cations and anions in electrode and electrolyte and a guiding design for the development of next‐generation high performance energy storage devices.     

Formation process and fractal growth model of HCFC-141b refrigerant gas hydrate

The microscopic visualization experiment on the formation process of HCFC-141b refrigerant gas hydrate has been investigated, and the morphological photos of hydrate formation process have been obtained. The results show that gas hydrate originally nucleated on the interface of refrigerant HCFC-141b and water under the condition of supercooling, then the hydrate grows continually due to the inducement of formed nucleation and diffusion of refrigerant. The formation of gas hydrate presents an arboreous phenomenon. The fractal dimension of the hydrate formation morphology on different stages was calculated. The calculating results indicate that the initial stage of the hydrate formation belongs to fractal growth, and the dimension is about 1.52. Based on the fractal theory, an RIN-DLA (random inducement nucleation-diffusion limited aggregation) model for the HCFC-141b hydrate growth was developed. The hydrate growth process was simulated with the developed model, and the fractal dimension for the simulated     

金属线电极分形生长的模拟

电沉积金属过程中,阴极沉积的金属边缘会出现包括枝晶生长在内的许多复杂形态,这会严重影响电沉积产品的质量和加工过程中的电流效率. 对枝晶分形生长的过程以及形貌进行研究,可以实现对沉淀物的可控生长. 本研究使用Python和Matlab软件相互结合,基于扩散限制凝聚（DLA）模型,建立平行线电极电沉积的模型. 通过分析不同粒子数、沉积概率、电极间距、运动步长、定向漂移条件下的分形生长的变化规律,以及模拟参数与实际电沉积因素对分形生长影响的内在联系,发现只要合理控制模拟的粒子数、沉积概率、线电极间距、运动步长、定向漂移概率参数即可与实际电化学体系的浓度和沉积时间、还原概率、两极间距、温度和电压、电极的相对位置和形状一一对应,从而模拟得到跟实际电沉积接近的分形图,最终可实现对分形生长的可控操作,对分形生长在工业电沉积等方面应用有很大的意义.     

Third‐order nonlinear optical properties of dendritic molecular aggregates: Effects of fractal architecture

We investigate the microscopic third‐order nonlinear optical properties, i.e., the second hyperpolarizabilities (γ), of two different sizes of molecular aggregates with a dendritic, i.e., Bethe‐lattice, structure. One possesses a nonfractal structure, while the other has a fractal structure. The aggregate is treated in a two‐exciton model composed of two‐state monomers coupled to each other by the dipole–dipole interaction. The off‐resonant γ of the aggregates are calculated by the numerical Liouville approach, including relaxation effects. The total γ value is partitioned into the contribution of virtual exciton generation, and its spatial contribution to γ is analyzed in relation to the virtual excitation processes in the perturbation theory. It is found that the intermolecular‐interaction effect enhances both one‐ and two‐exciton‐generation contributions, while the relaxation effect reduces those, although the one‐ and two‐exciton‐generation contributions have mutually opposite signs. From the comparison of spatial contributions to γ between the nonfractal and fractal aggregates, an enhancement of the contribution to γ from the periphery to the core is observed in the fractal structure, while such a feature is not observed in the nonfractal structure. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Hydronium‐Ion Batteries with Perylenetetracarboxylic Dianhydride Crystals as an Electrode

We demonstrate for the first time that hydronium ions can be reversibly stored in an electrode of crystalline 3,4,9,10‐perylenetetracarboxylic dianhydride (PTCDA). PTCDA exhibits a capacity of 85 mAh g⁻¹ at 1 A g⁻¹ after an initial conditioning process. Ex situ X‐ray diffraction revealed reversible and significant structure dilation upon reduction of PTCDA in an acidic electrolyte, which can only be ascribed to hydronium‐ion intercalation. The lattice expansion upon hydronium storage was theoretically explored by first‐principles density functional theory (DFT) calculations, which confirmed the hydronium storage in PTCDA.     

镉离子在H2SO4溶液中极谱行为的研究

本文研究了在没有动物胶的0.5M H_2SO_4溶液中镉离子的极谱行为,得到了如下的结果:(1)在0.050～20.0mM CdSO_4 0.5M H_2SO_4的十种溶液中测得的电流-电位曲线都有良好的波形、恒定的极限扩散电流和易于确定的半波电位.这些曲线上都没有极谱极大出现;其极限扩散电流(波高)与镉离子的浓度成正比.在镉离子低浓度(0.050～0.20mM)时,半波电位保持不变,在镉离子高浓度(1.00～20.0mM)时,也仅有很小的变化.故镉离子在0.5MH_2SO_4,溶液中的电流-电位曲线可供定量和定性测定之用.(2)镉离子在低浓度时的极谱波是一种可逆波.(3)前人在H_2SO_4溶液中研究镉离子时之所以没有能得到令人满意的极谱行为的原因是他们在H_2SO4溶液中添加了动物胶的缘故.(4)作者从得到的波形良好的电流-电位曲线上,测定了25±0.2℃时镉离子在0.5M H_2SO_4溶液中的扩散电流常数、半波电位和电极反应中得失的电子数.结果如下: i_d/cm~(2/3)t~(1/6)=3.97μA/mM·mg~(2/3)·s~(-1/2) E_(1/2)=-1.011V(0.5M硫酸亚汞电极)=-0.559V(饱和甘汞电极) n=2 这些数据比Lingane的数据,扩散电流常数2.6μA/mM·mg~(2/3)·s~(-1/2)和半波电位-0.59V(饱和甘汞电极)],要合理些.     

DEDUCTION OF QUASILATTICE WITH FIVE-FOLD SYMMETRY AND PARTICLE FRACTAL STRUCTURE MODEL

In the structure of quasicrystal, the coordination icosahedron has long ordering but no translation ordering. The author dealt with the building principle ofquasicrystal and thought that two principles played a certain role in the quasicrystal structure, i.e. the icosahedron principle and the golden mean principle. We obtained the most simple.structure model of quasicrystals, and could explain all details of the high-resolution electron microscopic image of the A1-Mn quasicrystal based on the two principles. The author's model has the characteristic of fractal structure, therefore, we call it the particle fractal structure madeh The author has made a systematic deduction of quasicrystal point group, forms, possible type of quasicrystal lattice.     

Growth kinetics of single copper crystals: the concentration dependence

The growth of single copper crystals electrodeposited on a tungsten electrode is studied at different concentrations of copper ions in the electrolyte solution. Information is obtained on the diffusion coefficient of copper ions, the exchange current density at the crystal-solution phase boundary and the charge transfer coefficient at a constant temperature.     

On the structure formation of hydrophobed particles in the boundary layer of water and octane phases

Two-dimensional aggregation of the surface modified glass beads was carried out in the boundary layer of water and octane phases. The effect of particles' hydrophobicity was investigated on the structure of forming aggregates and the growth process. The structure of the aggregates and their growth were characterized by a density function which demonstrates the change of mean particle density as a function of aggregate size. The growth yielded fractal or nonfractal structures in the investigated systems. The fractal structure of the aggregates was observed to be dependent on restructuring processes controlled by the surface properties of the beads.The experimental results are compared with earlier findings for aggregation of hydrophobic beads in the boundary layer of water and air phases.On leave from Loránd Eötvös University, Budapest, Hungary     

Fractal analysis of a discotic texture

The dendritic-type texture displayed by low molar mass discotic charge transfer systems possessing a columnar hexagonal ordered phase has been subjected to a fractal analysis. The diffusion limited aggregation approach was used to simulate the growth of the texture. The results are that the texture displays a fractal geometry and that the prominent features of the discotic texture are correctly reflected by the simulated clusters, including the fractal dimension. The conclusion is that the texture is conditioned by the lattice structure of the discotic phase and the kinetic processes, the sticking rules in the terms of diffusion limited aggregation model, responsible for the growth of the texture.     

Fractal metal nanoparticle aggregates morphology formation mediated by polyelectrolyte/surfactant complex films at interfaces

In this work, the gold nanoparticle self-assembly behavior of mica-surface-confined polyelectrolyte/surfactant complex films was investigated. First, modified partially hydrated polyacrylamide (MHPAM)/hexadecyltrimethylammonium bromide (CTAB) complex films were deposited on the mica surface using Langmuir–Blodgett technique. Then, the preadsorbed MHPAM/CTAB complex film mica plate was dipped into the gold aqueous solution and the interesting fractal nanostructured gold network was formed. In addition, the effect of dipping time on gold nanoparticle self-assembly morphology was studied. The mechanism of formation process is briefly proposed.     

金属锌电沉积过程的分形研究

对金属锌电沉积过程中的二维枝晶生长进行了研究,分析了外加电压、电解质浓度以及温度等实验条件对电沉积产物形貌及其分形维数的影响.结果表明,随着外加电压的增大,沉积产物形貌的变化趋势为由开放的分枝结晶向较为致密的生长形貌转变;随着硫酸锌浓度的增大,沉积产物具有分叉结构的致密纤维状枝晶簇和较为粗壮的开放型规则的分叉状枝晶,分形维数发生相应的变化;随着温度的升高,沉积产物的枝晶呈均匀化、致密化,沉积产物分形维数呈明显增大的趋势.     

Mathematical modeling of prolonged cycling of a porous cadmium electrode in alkaline power sources

An analysis of a computer model of a porous cadmium electrode is presented. The model describes prolonged cycling of the electrode under the alkaline battery conditions. It allows the evaluation of the dependence of the cathodic and anodic polarization on the concentration of the alkaline electrolyte, the charge and discharge current density, and the thickness and porosity of the electrode. The effect of the mass transfer of the active substance along the electrode thickness on the electrode capacity during the battery cycling can also be predicted. The calculations took into account that the cathodic and anodic processes on the cadmium electrode occurred by the liquid- and solid-state mechanisms. The diffusion, migration, and convective transport of the electrolyte components were also taken into account. An analysis of data using this model showed that it can be used in studies of the capacity of sintered cadmium electrodes under different operating conditions of nickel-cadmium batteries.     

Energetics during proton transfer process in hydrated zündel ion complex

Zündel ion (H₅O) is one of the two important structures formed during the proton transfer process in aqueous system. This work reports microsolvation of Zündel ion using density functional theory based B3LYP method with aug‐cc‐pVTZ basis set. Interaction of Zündel ion with four water molecules in its first solvation shell is studied using many‐body analysis approach. A change in many‐body energies and their contribution to the binding energy of a complex during the proton transfer process from donor to acceptor water molecule in Zündel ion‐4H₂O complex is obtained. For the hydrated Zündel ion complex, the contribution from total two‐body, three‐body, four‐body, five‐body, and relaxation energy to the binding energy is 84.7, 14, 6.87, 1.6, and 4%, respectively, at B3LYP/aug‐cc‐pVTZ level. Relaxation energy and total five‐body energy have repulsive contribution to the binding energy of a hydrated Zündel ion complex. It is found that the relaxation energy and binding energy of a Zündel‐4H₂O complex is the maximum and minimum, respectively, when a shared proton is at equal distance from oxygen atom of donor and acceptor water molecules. A significant change in two‐body, three‐body, and four‐body energies for which Zündel ion is one of the many‐body terms is observed during the proton transfer process. A change in total two‐body, total three‐body, total four‐body, and relaxation energy is about 2.6, 1.8, 0.4, and 1.1%, respectively, during the proton transfer process. A change in two‐body, three‐body, and four‐body interaction energies between water molecules is very small during the proton transfer process. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

阳极溶出伏安法中表面活性剂增敏机理探讨

本文探讨了表面活性剂在镉的阳极溶出伏安法中的增敏机理，认为表面活性剂可使训金属的水合子或其它络离子发生部分解离，既增加了溶液中电活性络离子的深度，又使离子的扩散速度加快，从而产生增敏作用。     

焦化过程半焦孔隙结构时空变化规律的实验研究——孔结构的分形特征及其变化

应用分形理论的概念，结合压汞法测得的半焦孔隙结构数据，建立孔结构分形特征模型，考察了焦化过程中不同焦化温度、不同横向空间位置半焦孔隙结构分形特征及其变化规律。结果表明，孔径大于5μm 的孔不具有分形特征，孔径为20nm～5μm孔的孔隙结构具有分形特征，其分形维数为2.45～2.83，可以用分形维数定量表征孔隙结构；相同空间位置下，半焦孔结构分形维数低温时较高，随温度逐渐升高先减小，然后增大再减小；同一空间位置不同温度下分形维数的变化量较小(< 0.15)，表明温度对半焦孔隙结构复杂程度的影响不明显；相同焦化温度下，半焦中心和边缘处的孔结构分形维数大于中间部位，表明中心位置和边缘位置处的孔隙结构要比中间位置处的复杂。     

A bidimensional simulation of particle-cluster aggregation with variable active sites particles

 In this work a simple program has been developed which simulates the process of particle– cluster aggregation limited by diffusion. All the simulation have been carried out using 2d square lattices with square “particles” having a variable number of active inter-action sites (from 3 to 8) for each particle in order to analyze the effect of such limitation on the fractal dimension of the aggregates. The fractal dimension of such aggregates was calculated by the so-called “box counting” method. It has been shown that there is no change in the value of the fractal dimension (1.70) as the active site number is increased. Instead it appears that there is an average number of active sites of about 2.3 for all the structures no matter how many active interaction sites the particles have. This appears as an interesting result in connection with the aggregation of particles such as renneted casein micelles, which could present differences in the surface density of active sites. Received: 11 February 1997 Accepted: 8 January 1998     

Effect of supporting electrolyte on the activation energy for diffusion of some monovalent ions

The effect of some alkali metal bromides, iodides and sulphates on the diffusion of bromide, iodide and thallium ions, respectively, is studied at various temperatures. The activation energy required for the process of diffusion of these three ions in different supporting electrolytes have been calculated. It is found that activation energy for a given ion decreases in the reverse order of the charge density of alkali metal ions of the supporting electrolyte. This observed trend in activation energy is explained qualitatively by considering the distortion in the water structure caused by these ions and agar molecules.