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.

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.

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.

Modelling two-layer nanofluid flow in a micro-channel with electro-osmotic effects by means of Buongiorno’s model

A fully developed steady immiscible flow of nanofluid in a two-layer microchannel is studied in the presence of electro-kinetic effects.Buongiorno’s model is employed for describing the behavior of nanofluids.Different from the previous studies on two-layer channel flow of a nanofluid,the present paper introduces the flux conservation conditions for the nanoparticle volume fraction field,which makes this work new and unique,and it is in coincidence with practical observations.The governing equations are reduced into a group of ordinary differential equations via appropriate similarity transformations.The highly accurate analytical approximations are obtained.Important physical quantities and total entropy generation are analyzed and discussed.A comparison is made to determine the significance of electrical double layer(EDL)effects in the presence of an external electric field.It is found that the Brownian diffusion,the thermophoresis diffusion,and the viscosity have significant effects on altering the flow behaviors.

Electrical Characteristics of Super Capacitors Using KOH Gel

Despite aqueous electrolytes having a low cost and excellent ionic conductivity,their low withstand voltage of 1.2 V makes them problematic for battery utility because that is a very important factor in battery production.In this research,the possibility of increasing the withstand voltage while maintaining the low cost of aqueous electrolytes was investigated.In this research,the solution electrolyte was made into a viscous solid polymer electrolyte to improve the withstand voltage of the electrolyte.A solid polymer electrolyte was made from sodium polyacrylate and doped with KOH(potassium hydroxide)and pure water.The improvement of the withstand voltage was evaluated by the specific capacitance.

Electric-double-layer-gated 2D transistors for bioinspired sensors and neuromorphic devices

Electric double layer(EDL)gating is a technique in which ions in an electrolyte modulate the charge transport in an electronic material through electrical field effects.A sub-nanogap capacitor is induced at the interface of electrolyte/semiconductor under the external electrical field and the capacitor has an ultrahigh capacitance density(~μF cm-2).Recently,EDL gating technique,as an interfacial gating,is widely used in two-dimensional(2D)crystals for various sophisti-cated materials characterization and device applications.This review introduces the EDL-gated transistors based on 2D materials and their applications in the field of bioinspired optoelectronic detection,sen-sing,logic circuits,and neuromorphic computation.

Enabling an Inorganic-Rich Interface via Cationic Surfactant for High-Performance Lithium Metal Batteries

An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.

Application of ionic liquids in single-molecule junctions:Recent advances and prospects

Single-molecule junctions,integrating individual molecules as active components between electrodes,serve as fundamental building blocks for advanced electronic and sensing technologies.The application of ionic liquids in single-molecule junctions represents a cutting-edge and rapidly evolving field of research at the intersection of nanoscience,materials chemistry,and electronics.This review explores recent advances where ionic liquids function as electrolytes,dielectric layers,and structural elements within single-molecule junctions,reshaping charge transport,redox reactions,and molecular behaviors in these nanoscale systems.We comprehensively dissect fundamental concepts,techniques,and modulation mechanisms,elucidating the roles of ionic liquids as gates,electrochemical controllers,and interface components in singlemolecule junctions.Encompassing applications from functional device construction to unraveling intricate chemical reactions,this review maps the diverse applications of ionic liquids in single-molecule junctions.Moreover,we propose critical future research topics in this field,including catalysis involving ionic liquids at the single-molecule level,functionalizing single-molecule devices using ionic liquids,and probing the structure and interactions of ionic liquids.These endeavors aim to drive technological breakthroughs in nanotechnology,energy,and quantum research.

Regulate electric double layer for one-step synthesize and modulate the morphology of(oxy)hydroxides

FeOOH have received considerable attention due to their natural abundance and cost-effectiveness.Despite the significant progress achieved,the one-step synthesis of integrated FeOOH is still a major challenge.Meanwhile,the current research on FeOOH catalyst still suffers from the unclear mechanism of controlling morphology.Here,density functional theory(DFT)calculations and X-ray photoelectron spectroscopy(XPS)demonstrated the strong electron-capturing and hydrogen absorption ability of Co in FeOOH,which further promotes the formation and stabilization of FeOOH.We used a one-step electrodeposition method to synthesize Co introduced FeOOH integrated electrocatalyst and propose to introduce ions with different valence states to regulate the morphology of FeOOH by precise modulation of electric double layer(EDL)composition and thickness.The prepared Co-FeOOH-K^(+)has a larger electrochemically active surface area(ECSA)(325 cm^(2))and turnover frequency(TOF)value(0.75 s^(-1)).In the electrochemical experiments of an alkaline anion exchange membrane electrolyzer,Co-FeOOH-K^(+)shows better oxygen evolution performance than commercial RuO_(2) under industrial production conditions and has good industrial application prospects.

EDLC charging performance for microgrid applications

In order to review storage performance of the electric double layer capacitor （EDLC） in microgrid applications, charging time and storage efficiency issues are mainly studied aiming at three different charging modes, including the constant voltage charging mode （CVCM）, the constant current charging mode （CCCM） and the constant power charging mode （CPCM）, based on the practical EDLC product. Numerical calculation methods are presented for different charging modes, and the charging efficiency is also reviewed with strict mathematical deductions, which is validated to be accurate enough and applicable through a simple case with the PV/EDLC system illustration. Finally, trade-off problems between charging time and energy loss are also studied. Research results show that the CPCM is more suitable for microgrid networks compared with the traditional constant-voltage and constant-current charging modes. The hybrid charging method is recommended to save energy and keep high efficiency relatively at the same time. However, how to manage the combination percentage of different charging modes in a reasonable way should be dealt with according to the practical requirements.

Hierarchically porous carbon foams for electric double layer capacitors

The growing demand for portable electronic devices means that lightweight power sources are increasingly sought after. Electric double layer capacitors （EDLCs） are promising candidates for use in lightweight power sources due to their high power densities and outstanding charge/discharge cycling stabilities. Three-dimensional （3D） self-supporting carbon-based materials have been extensively studied for use in lightweight EDLCs. Yet, a major challenge for 3D carbon electrodes is the limited ion diffusion rate in their internal spaces. To address this limitation, hierarchically porous 3D structures that provide additional channels for internal ion diffusion have been proposed. Herein, we report a new chemical method for the synthesis of an ultralight （9.92 mg/cm3） 3D porous carbon foam （PCF） involving carbonization of a glutaraldehyde- cross-linked chitosan aerogel in the presence of potassium carbonate. Electron microscopy images reveal that the carbon foam is an interconnected network of carbon sheets containing uniformly dispersed macropores. In addition, Brunauer-Emmett-Teller measurements confirm the hierarchically porous structure. Electrochemical data show that the PCF electrode can achieve an outstanding gravimetric capacitance of 246.5 F/g at a current density of 0.5 A/g, and a remarkable capacity retention of 67.5% was observed when the current density was increased from 0.5 to 100A/g. A quasi-solid-state symmetric supercapacitor was fabricated via assembly of two pieces of the new PCF and was found to deliver an ultra-high power density of 25 kW/kg at an energy density of 2.8 Wh/kg. This study demonstrates the synthesis of an ultralight and hierarchically porous carbon foam with high capacitive performance.