Probing the electric double layer structure at nitrogen-doped graphite electrodes by constant-potential molecular dynamics simulations

Electric double layer(EDL)is a critical topic in electrochemistry and largely determines the working performance of lithium batteries.However,atomic insights into the EDL structures on heteroatom-modified graphite anodes and EDL evolution with electrode potential are very lacking.Herein,a constant-potential molecular dynamics(CPMD)method is proposed to probe the EDL structure under working conditions,taking N-doped graphite electrodes and carbonate electrolytes as an example.An interface model was developed,incorporating the electrode potential and atom electronegativities.As a result,an insightful atomic scenario for the EDL structure under varied electrode potentials has been established,which unveils the important role of doping sites in regulating both the EDL structures and the following electrochemical reactions at the atomic level.Specifically,the negatively charged N atoms repel the anions and adsorb Li~+at high and low potentials,respectively.Such preferential adsorption suggests that Ndoped graphite can promote Li~+desolvation and regulate the location of Li~+deposition.This CPMD method not only unveils the mysterious function of N-doping from the viewpoint of EDL at the atomic level but also applies to probe the interfacial structure on other complicated electrodes.

Structure Regulation of Electric Double Layer via Hydrogen Bonding Effect to Realize High-Stability Lithium-Metal Batteries

The interfacial chemistry of solid electrolyte interphases(SEI)on lithium(Li)electrode is directly determined by the structural chemistry of the electric double layer(EDL)at the interface.Herein,a strategy for regulating the structural chemistry of EDL via the introduction of intermolecular hydrogen bonds has been proposed(p-hydroxybenzoic acid(pHA)is selected as proof-of-concept).According to the molecular dynamics(MD)simulation and density functional theory(DFT)calculation results,the existence of hydrogen bonds realizes the anion structural rearrangement in the EDL,reduces the lowest unoccupied molecular orbital(LUMO)energy level of anions in the EDL,and the number of free solvent molecules,which promotes the formation of inorganic species-enriched SEI and eventually achieves the dendrite-free Li deposition.Based on this strategy,Li‖Cu cells can stably run over 185 cycles with an accumulated active Li loss of only 2.27 mAh cm^(-2),and the long-term cycle stability of Li‖Li cells is increased to 1200 h.In addition,the full cell pairing with the commercial LiFePO_(4)(LFP)cathodes exhibits stable cycling performance at 1C,with a capacity retention close to 90%after 200 cycles.

Deep Penetration of Spudcan Foundation into Double Layered Soils

The spudcan foundation has been widely used in offshore engineering for jack-up rigs. However, “punch through' failure often occurs where a stronger soil layer overlays a softer soil layer. In this study, spudcan penetration into double layered soils is investigated numerically. The soil profile is set up as a stronger soil layer overlaying a softer soil layer, with the soil strength ratio (bottom soil strength / top soil strength) varied from 0.1 to 1.0 (1 means uniform soil). The bearing behaviour is discussed and the bearing capacity factors are given for various cases involving different layer thicknesses and different strength ratios of the two clay layers. The development of the plastic zones and the effect of soil self-weight on the bearing capacity are also discussed. From this study, it is found that, when a spudcan is distant from the soil layer boundary, the spudcan can be analysed with single soil layer data. However, when a spudcan becomes closer to the soil boundary layer, the influence of the lower soft soil layer is significant, and the bearing capacity of the spudcan decreases. The critical distance is an indication of the occurrence of “punch through' failure. The critical distance between the spudcan and the layer boundary is larger for a rough spudcan than the one for a smooth one, and the critical distance decreases with increasing soil strength ratio. The depth of cavity formed during initial spudcan penetration depends on the top layer soil strength, soil strength ratio and unit soil self-weight, and the cavity affects the spudcan bearing behaviour as well.

Hydrodynamic deep drawing of double layered conical cups

Hydrodynamic deep drawing assisted by radial pressure is an advanced sheet forming technology with great advantages such as higher drawing ratio, good surface quality and higher dimensional accuracy. In this process, both the bottom surface and the peripheral edge of sheets are under hydrodynamic pressure, so that the forming procedure is more uniform with low failure probability. Multi-layered sheets with complex geometries could be formed more easily with this technique compared with other traditional methods. Rupture is the main irrecoverable failure form in sheet forming processes. Prediction of rupture occurrence is of great importance for determining and optimizing the proper process parameters. In this research, a theoretical model was proposed to calculate the critical rupture pressure in production of double layered conical parts with hydrodynamic deep drawing process assisted by radial pressure. The effects of other process parameters on critical rupture pressure, such as punch tip radius, drawing ratio, coefficient of friction, sheet thickness and material properties were also discussed. The proposed model was compared with finite element simulation and validated by experiments on Al1050/St13 double layered sheets, where a good agreement was found with analytical results.

Study of axial double layer in helicon plasma by optical emission spectroscopy and simple probe

In this work we used a passive measurement method based on a high-impedance electrostatic probe and an optical emission spectroscope （OES） to investigate the characteristics of the double layer （DL） in an argon helicon plasma. The DL can be confirmed by a rapid change in the plasma potential along the axis. The axial potential variation of the passive measurement shows that the DL forms near a region of strong magnetic field gradient when the plasma is operated in wave- coupled mode, and the DL strength increases at higher powers in this experiment. The emission intensity of the argon atom line, which is strongly dependent on the metastable atom concentration, shows a similar spatial distribution to the plasma potential along the axis. The emission intensity of the argon atom line and the argon ion line in the DL suggests the existence of an energetic electron population upstream of the DL. The electron density upstream is much higher than that downstream, which is mainly caused by these energetic electrons.

Performance of Electric Double Layer Capacitors using Active Carbons Prepared from Petroleum Coke by KOH and Vapor Re-Etching

The electrochemical storage of energy in a special kind of active carbon materials used as capacitor electrodes is considered. Petroleum coke was used for preparation of carbons with different porosities by KOH and vapor etching with catalysis of FeCI3 in turn. Carbon electrodes were fabricated and used as electrodes of double layer capacitors. Nitrogen adsorption was used to characterize the porous structure of the carbons. The electrochemical performance of the capacitors in 6 mol/L KOH was investigated with constant current charge and discharge experiments. A specific capacitance larger than 160 F/g was achieved with an electrode composed of 75% active carbon with a specific surface area of 1180 m2/g and 20% graphite as conductive agent. Evaluation of capacitor performance was conducted by different techniques, e.g. voltammetry and impedance spectroscopy. Characteristics of the capacitor were also discussed. A hybrid power source consisting of nickel- hydrogen and double layer capacitor was demonstrated by powering successfully a simulated power load encountered in communication equipment.

Secondary Activation of Commercial Activated Carbon and its Application in Electric Double Layer Capacitor

The cheap commercial activated carbon (AC) was improved through the secondary activation under steam in the presence of FeCl2 catalyst in the temperature range of 800-950℃ and its application in electric double layer capacitors (EDLCs) with organic electrolyte was studied. The re-activation of AC results in the increases in both specific capacitance and high rate capability of EDLCs. For AC treated under optimized conditions, its discharge specific capacitance increases up to 55.65 F/g, an increase of about 33% as compared to the original AC, and the high rate capability was increased significantly. The good performances of EDLC with improved AC were correlated to the increasing mesoporous ratio.

Influence of Electric Double Layer on Lubrication

A mathematical model of lubrication with the electric double layer (EDL) was put forward in order to study the influence of EDL.The lubrication tests with a composite sliding block and a disk were carried out with oleic acid used as an additive to strengthen EDL.The streaming potential and friction force were measured. The experimental results show that the EDL has an apparent effect on the frictional force, which increases the ability of forming lubrication film.

Cylindrical and spherical Gardner solitons and double layers in a dusty electronegative non-thermal plasma with two-temperature electrons

A precise theoretical investigation has been made on the cylindrical and spherical （nonplanar） Gardner solitons （GSs） and double layers （DLs） in a dusty electronegative plasma （composed of inertial positive and negative ions, Maxwellian cold electrons, non-thermal hot electrons, and negatively charged static dust）. The reductive perturbation method has been used in derivation of the modified Gardner （MG） equation describing the nonlinear propagation of the dust ion-acoustic （DIA） waves. The MG equation admits solitary waves （SWs） and DLs solutions for σ around its critical value σ c （where σc is the value of σ corresponding to the vanishing of the nonlinear coefficient of the Korteweg de-Vries （K-dV） equation）. The nonplanar SWs and DLs solutions are numerically analyzed and the parametric regimes for the existence of the positive as well as negative SWs and negative DLs are obtained. The basic features of nonplanar DIA SWs and DLs, which are found to be different from planar ones, are also identified. The implications of our results to different space and laboratory dusty plasma situations, are discussed.

Development of mean-field electrical double layer theory

In order to understand the electric interfacial behavior, mean field based electric double layer （EDL） theory has been continuously developed over the past 150 years. In this article, we briefly review the development of the EDL model, from the dimensionless Gouy-Chapman model to the symmetric Bikerman-Freise model, and finally toward size-asymmetric mean field theory models. We provide the general derivations within the framework of Helmholtz free energy of the lattice- gas model, and it can be seen that the above-mentioned models are consistent in the sense that the interconversi0n among them can be achieved by reducing the basic assumptions.

RESISTANCE EFFECT OF ELECTRIC DOUBLE LAYER ON LIQUID FLOW IN MICROCHANNEL

Poisson-Boltzmann equation for EDL （electric double layer） and Navier- Stokes equation for liquid flows were numerically solved to investigate resistance effect of electric double layer on liquid flow in microchannel. The dimension analysis indicates that the resistance effect of electric double layer can be estimated by an electric resistance number, which is proportional to the square of the liquid dielectric constant and the solid surface zeta potential, and inverse-proportional to the liquid dynamic viscosity, electric conductivity and the square of the channel width. An ＂electric current density balancing＂ （ECDB） condition was proposed to evaluate the flow-induced streaming potential, instead of conventional ＂electric current balancing＂ （ECB） condition which may induce spurious local backflow in neighborhood of the solid wall of the microchannel. The numerical results of the flow rate loss ratio and velocity profile are also given to demonstrate the resistance effect of electric double layer in microchannel.

Study of the Electrical Double Layer of a Spherical Micelle: Functional Theoretical Approach

By using the iterative method in functional theory, an analytic expression of the Poisson-Boltzmann equation (PB eq.), which describes the distribution of the potential of electrical double layer of a spherical micelle, has been carried out under the general potential condition for the first time. The method also can give the radius, the surface potential, and the thickness of the layer.

Second-Order Discontinuities for Simple and Double Layers

Simple and double layers first appeared in electrostatics and later found various applications in mathematical physics. In this paper, we present the jump discontinuity conditions for their second-order spatial derivatives.

Comparison of double layer in argon helicon plasma and magnetized DC discharge plasma

We present in this paper the comparison of an electric double layer(DL)in argon helicon plasma and magnetized direct current(DC)discharge plasma.DL in high-density argon helicon plasma of 13.56 MHz RF discharge was investigated experimentally by a floating electrostatic probe and local optical emission spectroscopy(LOES).The DL characteristics at different operating parameters,including RF power(300-1500 W),tube diameter(8-60 mm),and external magnetic field(0-300 G),were measured.For comparison,DL in magnetized plasma channel of a DC discharge under different conditions was also measured experimentally.The results show that in both cases,DL appears in a divergent magnetic field where the magnetic field gradient is the largest and when the plasma density is sufficiently high.DL strength(or potential drop of DL)increases with the magnetic field in two different structures.It is suggested that the electric DL should be a common phenomenon in dense plasma under a gradient external magnetic field.DL in magnetized plasmas can be controlled properly by magnetic field structure and discharge mode(hence the plasma density).

A semi-analytical solution for electric double layers near an elliptical cylinder

A theoretical analysis on the electric double layer formed near the surface of an infinite cylinder with an elliptical cross section and a prescribed electric potential in an ionic conductor was performed using the linearized Gouy–Chapman theory. A semi-analytical solution in terms of the Mathieu functions was obtained. The distributions of the electric potential, cations, anions, and electric field were calculated. The effects of various physical and geometric parameters were examined. The fields vary rapidly near the elliptical boundary and are nearly uniform at far field. Electric field concentrations were found at the ends of the semi-major and semi-minor axes of the ellipse. These concentrations are sensitive to the physical and geometric parameters.

The superhydrophobic sponge decorated with Ni-Co double layered oxides with thiol modification for continuous oil/water separation

In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modification with n-dodecyl mercaptan(DDT). This method provides a new strategy to fabricate superhydrophobic PU sponge with a water contact angle of 157° for absorbing oil with low cost and in large scale. It exhibits the strong absorption capacity and highly selective characteristic for various kinds of oils which can be recycled by simple squeezing. Besides, the as-prepared sponge can deal with the floating and underwater oils, indicating its application value in handling oil spills and domestic oily wastewater. The good self-cleaning ability shows the potential to clear the pollutants due to the ultralow adhesion to water. Especially, the most important point is that the superhydrophobic sponge can continuously and effectively separate the oil/water mixture against the condition of turbulent disturbance by using our designed device system, which exhibit its good superhydrophobicity, strong stability.Furthermore, the SS-PU still maintained stable absorption performance after 150 cycle tests without losing capacity obviously, showing excellent durability in long-term operation and significant potential as an efficient absorbent in large-scale dispose of oily water.

Internal energy and specific antiferromagnetic heat in a ferromagnetic- double layers

The internal energy and specific heat of a Heisenberg ferro- antiferromagnetic double-layer system are studied by using spin-wave theory and the retarded Green function method at low temperatures. Numerical results show that the antiferromagnetic intralayer coupling J2 has an important influence on internal energy and specific heat for a four-sublattice system with antiferromagnetic （or ferrimagnetic） interlayer couplings.

Effect of N-doping-derived solvent adsorption on electrochemical double layer structure and performance of porous carbon

N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to characterize.Limited understanding of doping-derived EDL structure hinders insight into the structure-performance relations and the rational design of high-performance materials.Thus,we analyzed the mass and chemical composition variation of EDL within electrochemical operation by electrochemical quartz crystal microbalance,in-situ X-ray photoelectron spectroscopy,and time-offlight secondary ion mass spectrometry.We found that N-doping triggers specifically adsorbed propylene carbonate solvent in the inner Helmholtz plane(IHP),which prevents ion rearrangement and enhances the migration of cations.However,this specific adsorption accelerated solvent decomposition,rendering rapid performance degradation in practical devices.This work reveals that the surface chemistry of electrodes can cause specific adsorption of solvents and change the EDL structure,which complements the classical EDL theory and provide guidance for practical applications.

Magnetic Properties of Ferromagnetic Double Layers with Ferrimagnetic Interlayer Coupling at Zero Temperature

Spin-wave theory is used to study magnetic properties of ferromagnetic double layers with a ferrimagnetic interlayer coupling at zero temperature. The spin-wave spectra and four sublattices magnetizations and internal energy are calculated by employing retarded Green function technique. The sublattice magnetizations at ground state are smaller than their classical values, owing to the zero-point quantum fluctuations of the spins.

Thermal stability and data retention of resistive random access memory with HfOx/ZnO double layers

As an industry accepted storage scheme, hafnium oxide（HfO_x） based resistive random access memory（RRAM）should further improve its thermal stability and data retention for practical applications. We therefore fabricated RRAMs with HfO_x/ZnO double-layer as the storage medium to study their thermal stability as well as data retention. The HfO_x/ZnO double-layer is capable of reversible bipolar switching under ultralow switching current（〈 3 μA） with a Schottky emission dominant conduction for the high resistance state and a Poole–Frenkel emission governed conduction for the low resistance state. Compared with a drastically increased switching current at 120℃ for the single HfO_x layer RRAM, the HfO_x/ZnO double-layer exhibits excellent thermal stability and maintains neglectful fluctuations in switching current at high temperatures（up to 180℃）, which might be attributed to the increased Schottky barrier height to suppress current at high temperatures. Additionally, the HfO_x/ZnO double-layer exhibits 10-year data retention @85℃ that is helpful for the practical applications in RRAMs.