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.

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.

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.

Mitigating self-discharge of carbon-based electrochemical capacitors by modifying their electric-double layer to maximize energy efficiency

Self-discharge is a significant issue in electric double layer energy storage, which leads to a rapid voltage drop and low energy efficiency. Here, we attempt to solve this problem by changing the structure of the electric double layer into a de-solvated state, by constructing a nano-scale and ion-conductive solid electrolyte layer on the surface of a carbon electrode. The ion concentration gradient and potential field that drive the self-discharge are greatly restricted inside this electric double layer. Based on this understanding, a high-efficiency graphene-based lithium ion capacitor was built up, in which the self-discharge rate is reduced by 50% and the energy efficiency is doubled. The capacitor also has a high energy density, high power output and long life, and shows promise for practical applications.

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.

Electric Double layer Capacitor Based on Activated Carbon Material

In this study electric double layer capacitors (EDLCs) based on activated carbon material and organic electrolyte (tetraethyl ammonium tetrafluoroborate) were explored. The fabrication method for EDLC is presented and the performance of EDLC was examined by using the cyclic voltammetry, constant current charging and discharging technique, electrochemical impedance spectroscopy measurements. Influence of various components and design parameters on the performance of the capacitors were preliminarily investigated. Up to now, EDLC based on carbon materials can deliver 20.7 W/kg at the discharge rate of I =0.3 mA, together with the energy density of 8.5 Wh/kg. Equivalent series resistance (ESR) is 0.716 Ω·cm 2. The specific power of the capacitor is low and further attempts to raise the power capability of the capacitors are necessary. Some considerations are put forward to further improve the performance of EDLC.

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.

Characterization of Microporous Activated Carbon Electrodes for Electric Double-layer Capacitors

Activated carbons(ACs) with a wide range of surface areas were made from petroleum coke by means of KOH activation. The electrochemical characterization was carried out for several activated carbons used as polarizable electrodes of electric double-layer capacitors(EDLCs) in an aqueous electrolytic solution. The porous structures and electrochemical double-layer capacitance of the activated carbons were investigated by virtue of nitrogen gas adsorption and constant current cycling(CCC) methods. The relationship among the surface area, pore volume of the activated carbons and specific double-layer capacitance was discussed. It was found that the specific capacitance of ACs increased linearly with the increase of surface area. The presence of mesopores in the activated carbons with very high surface area(>2000 m\+2/g) was not very effective for them to be used as EDLCs. The influence of chemical characteristics of the activated carbons on the double layer formation could be considered to be negligible.

Empirical formulae for electric double-layer repulsion between two arbitrarily inclined clay particles

To understand the mesoscopic mechanism of clayey soil in view of macroscopic behavior, it is essential to quantitatively calculate the electric double-layer repulsion between arbitrarily inclined clay particles.However, suitable calculation methods with high efficiency and accuracy are still rare at present in literature. Based on a great number of numerical calculations of the repulsion between two inclined platy clay particles, explicit empirical formulae for estimating electric double-layer repulsion between clay particles are put forward. Comparison between the empirical solutions and corresponding numerical results shows that the proposed formulae have a reasonable accuracy, and application of the presented formula is easy and efficient.

Adsorption of K^+ from an aqueous phase onto an activated carbon used as an electric double-layer capacitor electrode

The adsorption capacity and absorption rate for electrolyte onto activated carbon are important parameters used to characterize activated carbon electric double-layer capacitor electrodes. In this paper the pore structure of typical commercial activated carbons, and various Mn-doped activated carbons prepared on a laboratory scale, are described. The pore structure was character-ized by N2 adsorption/desorption isotherms. Isotherms for K+ adsorption onto these activated carbons from the aqueous phase were also obtained. The experimental, equilibrium K+ adsorption data were fitted to the Langmuir, Freundlich or Temkin equations. Adsorption of K+ onto the activated carbons was measured and plotted as a function of time. The adsorption kinetic data were modeled by either pseudo-first or pseudo-second order equations. The Elvoich equation, a liquid film diffusion and an intra-particle diffusion model were used to fit the kinetic data. The results indicate that the adsorption of K+ onto activated carbon is influenced by many factors including pore size distribution, specific surface area and the surface chemistry of the activated carbons. The Temkin equation best describes the equilibrium adsorption data. The pseudo-second order model exactly describes the whole adsorption process, which is controlled by both liquid film and intra-particle diffusion.

Carbon aerogels for electric double-layer capacitors

In this study, carbon aerogels were derived via the pyrolysis of resorcinol-formaldehyde (RF) aerogels, which were cost-effectively manufactured from RF wet gels by an ambient drying technique instead of conventional supercritical drying. By varying the R/C ratio (molar ratio of resorcinol to catalyst), mesoporous carbon aerogels with high specific surface area were prepared successfully and further investigated as electrode materials for electric double-layer capacitors (EDLCs). The textural properties of carbon aerogels obtained were characterized by nitrogen adsorption/desorption analysis and SEM. The electrochemical performances of carbon aerogels were investigated by impedance spectroscopy, galvanostatic charge/discharge and cyclic voltammetry methods. The results show that BET surface area and specific capacitance increase with R/C ratio, the maximum values of 727 m2·g-1 and 132 F·g-1 are achieved at R/C ratio will of 300. Increasing R/C ratio increase the average pore size of carbon aerogel electrode, which has improved the rate capability. Furthermore, EDLC with carbon aerogel electrodes has an excellent stability at large discharge current and long cycle life.

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.

Synergistic interaction between redox-active electrolytes and functionalized carbon in increasing the performance of electric double-layer capacitors

The increasing demand of high-performance supercapacitors has aroused great interest in developing specific capacitance and energy density. Active carbon （AC） has attracted much attention as a promising electrode material for electric double-layer capacitors （EDLCs）. Here, a facile strategy has been employed to fabricate high-performance EDLCs using the surface-oxygen functionalized active carbon （FAC） as an electrode and 2 M KOH with K3Fe（CN）6 as an electrolyte. In this system, K3Fe（CN）6 was used as a redox additive to enhance the performance of EDLCs. A 38.5% increase in specific capacitance （207.7 F g-1） was achieved compared with the KOH electrolyte without adding K3Fe（CN）G （152.9 F g-1）, due to the synergistic effects between oxygenic functional groups and redox electrolyte. These findings provide an alternative route to improve the performance of EDLCs, which are promising candidates for the broad applications of high-performance supercapacitors.

Curvature effects on electric-double-layer capacitance

Understanding the microscopic structure and thermodynamic properties of electrode/electrolyte interfaces is central to the rational design of electric-double-layer capacitors(EDLCs).Whereas practical applications often entail electrodes with complicated pore structures,theoretical studies are mostly restricted to EDLCs of simple geometry such as planar or slit pores ignoring the curvature effects of the electrode surface.Significant gaps exist regarding the EDLC performance and the interfacial structure.Herein the classical density functional theory(CDFT)is used to study the capacitance and interfacial behavior of spherical electric double layers within a coarse-grained model.The capacitive performance is associated with electrode curvature,surface potential,and electrolyte concentration and can be correlated with a regression-tree(RT)model.The combination of CDFT with machine-learning methods provides a promising quantitative framework useful for the computational screening of porous electrodes and novel electrolytes.

Application of Nanofiber Fabricated by Cotton Candy Method to Electric Double-Layer Capacitor

In recent years, application of carbon-based nano material to electrode material has been paid attention, however, due to its higher cost, it would be difficult to put it into practical use. Then, we have proposed to make nano carbon fiber with lower production cost. The purpose of our research was, to apply our nano carbon fiber to electrical double-layer capacitor electrode. We used cotton candy method to make nano fiber, and applied microwave heating for carbonization. By applying nano carbon fiber to electrical double-layer capacitor electrode, we got results that thicker electrode containing nano carbon fiber leads to lower resistance value, compared with electrode without containing nano carbon fiber. From this result, it was indicated that by containing nano carbon fiber, the electric bypass was formed in the electrode.

Theoretic analysis and experiment of electric nano-double layer on electro-absorption desalination process

The relationships between electrode absorptive capacity and solution temperature,concentration and electrode potential were investigated by theoretic analysis and experiments.The results show that the charge of electric double-layer on electrode interface is very sensitive to temperature and electrode potential in the electroadsorption process.For the specific electrical adsorption device,the electrode potential must be controlled to avoid the electrolytic reaction.

Tuning the phase separation in La_(0.325)Pr_(0.3)Ca_(0.375)MnO_3 using the electric double-layer field effect

Electric double-layer field effect experiments were performed on ultrathin films of La0.325Pr0.3Ca0.375MnO3, which is noted for its micrometer-scale phase separation. A clear change of resistance up to 220% was observed and the characteristic metal-insulator transition temperature Tp was also shifted. The changes of both the resistance and Tp, suggest that the electric field induced not only tuning of the carrier density but also rebalancing of the phase separation states. The change of the charge-ordered insulating phase fraction was estimated to be temperature dependent, and a maximum of 16% was achieved in the phase separation regime. This tuning effect was partially irreversible, which might be due to an oxygen vacancy migration that is driven by the huge applied electric field.

Candidate organic electrolytes for electric double-layer capacitor application

Electrolytic conductivity, viscosity and electrochemical behavior were investigated for organic electrolytes based on PC（Propylene carbonate）, MAN（Methoxy acetonitrile） and GBL（γ-Butyrolactone） solvents. It was found that 1 mol/L Et4NBF4-MAN had the highest conductivity, lowest viscosity and acceptable potential window. The specific capacitance and energy density obtained from the capacitor using 1 mol/L Et4NBF4-MAN as electrolyte were the highest among all the tested electrolytes.（1 mol/L） Et4NBF4-GBL also seemed promising to be used in electric double-layer capacitor （EDLCs）.