Dynamic diffuse double-layer model for the electrochemistry of nanometer-sized electrodes

A dynamic diffuse double-layer model is developed for describing the electrode/electrolyte interface bearing a redox reaction. It overcomes the dilemma of the traditional voltammetric theories based on the depletion layer and Frumkin's model for double-layer effects in predicating the voltammetric behavior of nanometer-sized electrodes. Starting from the Nernst-Planck equation, a dynamic interfacial concentration distribution is derived, which has a similar form to the Boltzmann distribution equation but contains the influence of current density. Incorporation of the dynamic concentration distribution into the Poisson and Butler-Volmer equations, respectively, produces a dynamic potential distribution equation containing the influence of current and a voltammetric equation containing the double-layer effects. Computation based on these two equations gives both the interfacial structure (potential and concentration profiles) and voltammetric behavior. The results show that the electrochemical interface at electrodes of nanometer scales is more like an electric-double-layer, whereas the interface at electrodes larger than 100 nm can be treated as a concentration depletion layer. The double-layer nature of the electrode/electrolyte interface of nanometer scale causes the voltammetric responses to vary with electrode size, reactant charge, the value of formal redox potential, and the dielectric properties of the compact double-layer. These voltammetric features are novel in comparison to the traditional voltammetric theory based on the transport of redox molecules in the depletion layer.     

Influence of electrical double-layer interaction on coal flotation

In the early 1930s it was first reported that inorganic electrolytes enhance the floatability of coal and naturally hydrophobic minerals. To date, explanations of coal flotation in electrolytes have not been entirely clear. This research investigated the floatability of coal in NaCl and MgCl2 solutions using a modified Hallimond tube to examine the role of the electrical double-layer interaction between bubbles and particles. Flotation of coal was highly dependent on changes in solution pH, type of electrolyte, and electrolyte concentration. Floatability of coal in electrolyte solutions was seen not to be entirely controlled by the electrical double-layer interaction. Coal flotation in low electrolyte concentration solutions decreases with increase in concentration, not expected from the theory since the electrical double layer is compressed, resulting in diminishing the (electrical double layer) repulsion between the bubble and the coal particles. Unlike in low electrolyte concentration solutions, coal flotation in high electrolyte concentration solutions increases with increase in electrolyte concentration. Again, this behavior of coal flotation in high electrolyte concentration solutions cannot be quantitatively explained using the electrical double-layer interaction. Possible mechanisms are discussed in terms of the bubston (i.e., bubble stabilized by ions) phenomenon, which explains the existence of the submicron gas bubbles on the hydrophobic coal surface.     

Self-discharge characteristics of an electric double-layer capacitor with polymer hydrogel electrolyte

An electric double-layer capacitor (EDLC) was assembled with the polymer hydrogel electrolyte prepared from cross-linked potassium poly(acrylate) (PAAK) and KOH aqueous solution, and the self-discharge characteristics were investigated. The EDLC cell with the polymer hydrogel electrolyte showed lower voltage decay on open circuit than that with a KOH aqueous solution. Moreover, it was found that the leakage current of the EDLC cell was markedly suppressed by using the polymer hydrogel electrolyte. The suppression was enhanced with increasing PAAK content in the electrolyte. These results strongly suggest that the PAAK plays an important role in the suppression of self-discharge.     

The similarity of electric double-layer interaction from the general Poisson-Boltzmann theory

We studied electric double-layer (EDL) interactions in electrolytes with different valence combinations. Our results show that the interactions are similar for electrolytes with the same co-ion valences and concentrations and such similarity increases with the co-ion valence and surface potential. A scaled surface potential was defined and found to be useful in characterizing the difference in EDL interaction. These results show that co-ions play a more important role than counterions in determining EDL potential and interaction in an electrolyte solution, especially for systems with high co-ion valence and/or high surface potentials.     

Computer simulation of active layers in double-layer supercapacitors: Galvanostatics,determination of effective coefficients,and calculation of overall characteristics

A computer simulation of the structure and modes of functioning of biporous active layers (activated carbon) in double-layer capacitors (DLCs) was performed. The charging of DLCs in a galvanostatic mode was studied. The main characteristics of DLCs (charging time, specific capacity, stored energy, and power) were calculated. DLCs with aqueous electrolyte of different types were studied: active layer with the “ideal” structure (type 1), active layer with a monoporous structure (2), and biporous active layer (3). A computer simulation of biporous active layers of DLCs involves the formulation of a model of the structure of the active layer, percolation evaluation, and calculation of the effective ion conductivities of both highly porous carbon grains and the whole active layer. When calculating the characteristics of the active layers of DLC, we analyzed the effect of the main parameters (charge current density and active layer thickness) on the charging process and overall characteristics. The central problem of calculation of a DLC with a real, nonmonoporos structure was formulated. In active layers generally having pores of three types (micro-, meso-, and macropores) in the galvanostatic mode of DLC charging, the wide pores are polarized first. In this case, the limiting acceptable potential is achieved, and galvanostatic charging should be stopped and changed to potentiostatic charging. As a result, a large number of micropores can remain unpolarized. Therefore, it is important to perform a theoretical search for means to carry out complete adsorption of ions in micropores and obtain high specific capacities of DLCs.     

Determination of electrical double-layer parameters for the adsorption of neutral molecules at the electrode–solution interface

The study of the structure of the electrode–solution interface usually involves the measurement of the differential capacity–potential characteristics of the system. In order to obtain the double-layer parameters from these data, integration and differentiation procedures are required and, for this purpose, the use of computational methods is of great value. Two computer programs have been written for the treatment of data for the adsorption of neutral molecules on electrodes. The programs use the charge density and the electrode potential as the electrical variable, respectively, and, in both cases, the differentiation procedures have been optimized by the use of an adequate numerical function. The advantages of doing a simultaneous analysis on both electrical variables are pointed out.     

Carbon/carbon supercapacitors

Supercapacitors, or electrochemical capacitors, are a power storage system applied for harvesting energy and delivering pulses during short periods of time. The commercially available technology is based on charging an electrical double-layer (EDL), and using high surface area carbon electrodes in an organic electrolyte. This review first presents the state-of-the-art on EDL capacitors, with the objective to better understand their operating principles and to improve their performance. In particular, it is shown that capacitance might be enhanced for carbons having subnanometric pores where ions of the electrolyte are distorted and partly desolvated. Then, strategies for using environment friendly aqueous electrolytes are presented. In this case, the capacitance can be enhanced through pseudo-faradaic contributions involving i) surface functional groups on carbons, ii) hydrogen electrosorption, and iii) redox reactions at the electrode/electrolyte interface. The most promising system is based on the use of aqueous alkali sulfate as electrolyte allowing voltages as high as 2 V to be reached, due to the high overpotential for di-hydrogen evolution at the negative electrode.     

The influence of crystallographic inhomogeneity of a polycrystalline electrode surface on the behavior of the electric double-layer

The specific features of the electric double-layer structure at polycrystalline electrodes in the absence of specific ion adsorption have been examined for two different models: Model I and Model II. In the case of Model I each of the faces showing on the surface of a polycrystalline electrode retains its own Helmholtz and diffuse double layers. In the case of Model II the faces retain only their own Helmholtz layer, whereas the diffuse layer is common to the entire electrode surface. The difference of zero charge potentials of the faces is defined both by their dissimilar hydrophilic properties and by different work functions. The experimental data available at present on the electric double-layer structure at polycrystalline electrodes for which the potentials of zero charge of the faces differ significantly are described by Model I.     

Magnetohydrodynamic effects on a charged colloidal sphere with arbitrary double-layer thickness

An analytical study is presented for the magnetohydrodynamic (MHD) effects on a translating and rotating colloidal sphere in an arbitrary electrolyte solution prescribed with a general flow field and a uniform magnetic field at a steady state. The electric double layer surrounding the charged particle may have an arbitrary thickness relative to the particle radius. Through the use of a simple perturbation method, the Stokes equations modified with an electric force term, including the Lorentz force contribution, are dealt by using a generalized reciprocal theorem. Using the equilibrium double-layer potential distribution from solving the linearized Poisson-Boltzmann equation, we obtain closed-form formulas for the translational and angular velocities of the spherical particle induced by the MHD effects to the leading order. It is found that the MHD effects on the particle movement associated with the translation and rotation of the particle and the ambient fluid are monotonically increasing functions of κa, where κ is the Debye screening parameter and a is the particle radius. Any pure rotational Stokes flow of the electrolyte solution in the presence of the magnetic field exerts no MHD effect on the particle directly in the case of a very thick double layer (κa→0). The MHD effect caused by the pure straining flow of the electrolyte solution can drive the particle to rotate, but it makes no contribution to the translation of the particle.     

Saturation of subnanometer pores in an electric double-layer capacitor

Improvements in the energy density of electric double-layer capacitors (EDLCs) can in particular be gained by enhancing their capacitance. Recent findings suggest that the specific capacitance can be increased by matching the sizes of pores and desolvated ions. However, on such matching, we evidenced that charge storage saturation can occur in organic electrolyte before reaching the maximum voltage, e.g. 2.7 V, due to the insufficiently developed porosity. The experimental charge is larger than the calculated on account of the size of rigid cations, because of the intercalation-like behaviour and/or distortion of ions. The experimental and calculated values are less coincident for the higher sweep rates, which reveals that the optimal average pore size should depend on the current load, tending to shift to higher values in the normal usage conditions of supercapacitors.     

Effect of porous structure of activated carbon electrodes on characteristics of double-layer supercapacitors

Porous structure of electrode materials was studied and the role played by macroporous in electrodes of model double-layer supercapacitors was experimentally analyzed. It was shown that the excess macropore volume in electrodes has an adverse effect and, on the whole, reduces in a complicated way the specific electrochemical characteristics of these devices. This makes necessary to develop the optimal electrode structure as regards not only nanoporous, but also macroporous structure.     

Stability of Carbons in the Composition of Electrodes for Supercapacitors with Organic Electrolytes

The stability of double-layer supercapacitors with organic electrolyte and electrodes of activated charcoal is improved by optimizing the activation parameters of the material and also by its additional thermal treatment after the activation. The optimized modes of such pretreatment are shown.     

计算模拟在锂金属负极研究中的应用

锂金属以其高比容量和低电极电势,在高能量密度电池领域具有极大潜力,然而界面反应复杂、枝晶生长难以抑制等问题,导致电池易燃易爆、容易击穿短路,极大地限制了锂电池的应用。计算模拟有助于科研工作者认识反应机理、预测筛选电极材料以及优化电池设计,与实验相辅相成。本文对近年计算模拟在锂金属电极中的应用进行综述,重点在于利用分子动力学、第一性原理计算等计算方法,研究界面反应、固体电解质膜以及锂形核。此外,新开发的固态电解质很好地解决了传统锂电池易燃易爆等问题,提高了能量密度,但也存在界面阻力大、传导性能差以及枝晶生长等问题,对此,我们就计算模拟在固态电解质锂电池中锂负极的应用进行综述。最后,我们论述了该领域潜在研究方向。     

高容量超级电容器电极材料的设计与制备

超级电容器寿命长,安全性高,并可以实现快速充放电,是化学电源研究的热点之一。然而,超级电容器的能量密度较低限制了其更多的应用。因此,超级电容器领域的研究关注点在如何提高超级电容器的能量密度。其中,提高比容量是提高能量密度的一种有效途径。本文通过对电极材料和电解液的优化来研究制备得到高容量超级电容器的方法。电极材料的比表面积、孔道结构和导电性对其电化学性能有着直接的影响。一方面,通过优化电极材料的孔道结构和比表面积可以增加活性位点并提高电解液离子传导率,从而得到高比电容。另一方面,电极材料导电性的提高有利于提升其电子传导率从而得到较高的比容量。本文分别对碳材料和金属氧化物/氢氧化物的优化达到了增加双电层电容和赝电容的目的。不仅如此,还可以通过在电解液中增加氧化还原电对从而得到高比电容。这一方法为高容量超级电容器的制备提供了新的思路。     

Effects of double-layer polarization and electroosmotic flow on the electrophoresis of an ellipsoid in a spherical cavity

The electrophoresis of a rigid, positively charged ellipsoidal particle at the center of a spherical cavity is investigated theoretically under the conditions where the effects of double-layer polarization and the presence of an electroosmotic flow can be important. The equations governing the problem under consideration and the associated boundary conditions are solved numerically, and the influences of the key parameters on the electrophoretic mobility of the particle are discussed. We show that if the cavity is uncharged, the effect of double-layer polarization yields a local minimum in the electrophoretic mobility as the thickness of the double layer varies. This local minimum disappears if the cavity is also positively charged. In addition to reducing the scaled mobility of an ellipsoid, the presence of the boundary is also capable of influencing the relative magnitudes of the scaled mobility for particles of various shapes. For instance, if the volume of an ellipsoid is fixed, the scaled mobility ranks as prolate > sphere > oblate if the boundary effect is unimportant, but that order is reversed if the boundary effect is important.     

CdS and CdSe quantum dots subsectionally sensitized solar cells using a novel double-layer ZnO nanorod arrays

We report a novel approach for synthesizing CdS and CdSe quantum dots subsectionally sensitized double-layer ZnO nanorods for solar cells, which are comprised of CdS QDs-sensitized bottom-layer ZnO NRs and CdSe QDs-sensitized top-layer ZnO NRs. X-ray diffraction study and scanning electron microscopy analysis indicate that the solar cells of subsectionally sensitized double-layer ZnO NRs, which are the hexagonal wurtzite crystal structure, have been successfully achieved. The novel structure enlarged the range of absorbed light and enhanced the absorption intensity of light. The I-V characteristics show that the double-layer structure improved both the current density (J_sc) and fill factor (FF) by 50%, respectively, and power conversion efficiency (η) was increased to twice in comparison with the CdS QDs-sensitized structure.     

Control of the structure of self-spreading lipid membrane by changing electrolyte concentration

We have controlled the structure of self-spreading lipid bilayer membranes prepared on surface-oxidized silicon substrates by changing electrolyte concentration. Analysis of the fluorescence intensity, considering the optical interference effect, clarified the stacking structure of the lipid membrane. By varying the electrolyte concentration, we can vary the number of single multilamellar lobes adsorbed on the underlying self-spreading bilayer. This dependence of the stacking ability on the electrolyte concentration was investigated on the basis of changes in the bilayer-lobe interaction energies, including van der Waals, electrostatic double layer, and hydration interaction energies. Theoretical estimation suggests that the observed electrolyte concentration dependence can be explained by the combination of the van der Waals attractive interaction energy and the repulsive double-layer interaction energy.     

Design of hierarchical double-layer NiCo/NiMn-layered double hydroxide nanosheet arrays on Ni foam as electrodes for supercapacitors

Reasonably designing the structure of composite materials and effectively increasing electroactive sites of electrode materials are considered as the promising approaches to enhance the electrochemical performance for supercapacitors. Herein, a double-layer layered double hydroxide nanosheet array grown on Ni foams is constructed through a facile two-step hydrothermal method. The as-prepared double-layer electrode materials including Ni, Co, and Mn elements possess large surface area and porosity; thus, it can increase the contact between electrolytes and the electrode materials, which leads to an increase in electroactive sites and high electrochemical performance. The double-layer electrode shows a high capacitance performance (2950 F/g at 1 A/g) and superior cycling stability (79% retention after 10,000 cycles at 10 A/g). In addition, the asymmetric NiCo/NiMn-LDHs//AC device is fabricated and manifests good capacity with excellent cyclic stability of 82.2% after 10,000 cycles.     

Optically compensated double-layer electrically controlled birefringence liquid crystal display with wide-viewing-angle cone

An electrically controlled birefringence liquid crystal display has a problem over narrow viewing angle. To solve this problem, the authors proposed a double-layer electrically controlled birefringence liquid crystal display with a wide-viewing-angle cone under an applied voltage. In this device, each liquid crystal layer compensates the variation of retardation as a function of viewing angle. However, the optical compensation occurs only when certain voltages are applied. The objective of this paper is to propose a novel film compensated double-layer electrically controlled birefringence liquid crystal display that has a wide cone of view in any state. This device is based on the concept of compensation of retardation.     

Potential-induced structural deformation at electrode surfaces

The atomic structure on the metal side of the electrochemical interface depends on the applied electric potential and the nature of the adsorbing species in the electrolyte solution. In this short article, we review some recent results probing surface stress and surface relaxation effects in single-crystal metal electrodes that are driven by potential changes. Both the potential and the structure in the electrolyte layers at the interface alter the metal electronic structure so that the surface in the electrochemical environment is strongly modified from the ultra-high vacuum counterpart. A methodology for linking experimental and theoretical approaches for a fundamental understanding of electrochemical reactions is proposed.