Model Of Electrical Double Layer Research Articles

Activation Energy of Ion Desorption at Ionic Liquid/Pt Electrode Interfaces: A Sum-Frequency Generation Vibrational Spectroscopic Study.

Electrolyte/electrode interfaces of room-temperature ionic liquids (RTILs) exhibit hysteretic responses to different applied potentials owing to the differences in the ion adsorption/desorption processes; the ion desorption requires excess potential, which reflects the activation energy of ion desorption. Thus far, the contributions of the ion adsorption energy and the activation barrier for ion desorption toward the ion-dependent excess potential have not been quantified. Herein, we report on our infrared-visible sum-frequency generation vibrational spectroscopy study of the hysteretic responses of the anion adsorption/desorption at Pt electrode interfaces using neat, binary, and diluted RTILs composed of 1-butyl-3-methylimidazolium cations ([C4mim]+) and bis(trifluoromethanesulfonyl)amide ([TFSA]-) and trifluoromethanesulfonate ([OTf]-) anions. Experimental results are compared to the theoretical calculations for the electric double layer model. The hysteretic response of the RTIL/Pt interface derives predominantly from the activation energy of anion desorption, which causes the negative excess potential required for anion desorption. A comparison of the anion adsorption/desorption behaviors of neat RTILs with those of binary and diluted RTILs reveals that the large activation energy of anion desorption at the neat RTIL/Pt interface originates largely from the activation barrier for restructuring ionic layering in the diffuse layer.

Corrosion Behavior of X80 Steel in a Simulated Soil Solution Under Square-Wave Current Interference

The buried pipeline is disturbed by the dynamic direct current (DC) stray current with the subway as the main leakage source, which has the safety risk of accelerating corrosion, resulting in pipeline failure, which not only causes economic losses but also threatens personal safety. Therefore, it is necessary to study the corrosion behavior of pipeline steel under dynamic DC interference. The corrosion behavior of X80 steel under dynamic DC interference were studied by a mass loss test, alternating current impedance, circuit simulation, x-ray diffraction, and a Pourbaix diagram. Combined with the corrosion efficiency and Pourbaix diagram of the Fe-H2O system, the reversible process and reduction process mechanism in the Faraday process are proposed. The reason why the corrosion efficiency slows down in the process of non-Faraday is analyzed by the electric double-layer model of equivalent circuit calculation. In addition, based on the above corrosion process, the corresponding conceptual model of the corrosion mechanism is proposed. The experimental results show that with the asymmetry of positive and negative half-cycle interference duration and the increase of current density, the corrosion efficiency, and current corrosion efficiency of X80 steel decrease, and local corrosion intensifies. The length of the negative half-cycle interference affects the capacitive charge-discharge effect at the metal/solution interface and the reduction reaction process of corrosion products, resulting in corrosion slowing down and corrosion efficiency reduction. This is also an important reason for the reduction of corrosion mass loss observed in the experiment compared with steady-state DC.

Beyond the electrical double layer model: ion-dependent effects in nanoscale solvent organization.

The nanoscale organization of electrolyte solutions at interfaces is often described well by the electrical double-layer model. However, a recent study has shown that this model breaks down in solutions of LiClO4 in acetonitrile at a silica interface, because the interface imposes a strong structuring in the solvent that in turn determines the preferred locations of cations and anions. As a surprising consequence of this organisation, the effective surface potential changes from negative at low electrolyte concentration to positive at high electrolyte concentration. Here we combine previous ion-current measurements with vibrational sum-frequency-generation spectroscopy experiments and molecular dynamics simulations to explore how the localization of ions at the acetonitrile-silica interface depends on the sizes of the anions and cations. We observe a strong, synergistic effect of the cation and anion identities that can prompt a large difference in the ability of ions to partition to the silica surface, and thereby influence the effective surface potential. Our results have implications for a wide range of applications that involve electrolyte solutions in polar aprotic solvents at nanoscale interfaces.

(Invited) Modeling of the Electric Double Layer (EDL) at Li/SEI/Electrolyte Interfaces

Liquid electrolytes, consisting of salts, solvents, and additives, must form a stable solid electrolyte interphase (SEI) to ensure the performance and durability of lithium(Li)-ion batteries. However, the electric double layer (EDL) structure near charged surfaces is still unsolved, despite its importance in dictating the species being reduced for SEI formation near a negative electrode. Recently, we have developed an interactive Molecular Dynamics -Density Functional Theory -data statistics (MD-DFT-data) model to investigate the reduction reactions of multicomponent electrolytes within the EDL. We will illustrate the effect of EDL on SEI formation in two essential electrolytes, the carbonate-based electrolyte for Li-ion batteries and the ether-based electrolyte for batteries with Li-metal anodes. Our results reveal that the role of fluoroethylene carbonate (FEC) additive differs drastically in the two electrolytes as an SEI modifier to form the beneficial F-containing SEI component (e.g., LiF). The competition among the cations, anions, and various species in the solvents with a charged surface at different temperatures can all jointly determine the EDL structure and therefore the SEI compositions. [1]While the classical Poisson–Boltzmann EDL model developed for fully solvated ions face new challenges in high-concentration liquid electrolytes (HCE), localized high-concentration liquid electrolytes (LHCE) as well as solid electrolytes (SE), new theoretical developments are required. We will introduce a new DEL model in SE and SEI by solving the DFT-informed Poisson–Fermi–Dirac equation and demonstrate how it can be used for interlayer thickness design. [2][1] Wu, Q.S, McDowell, M.T., & Qi, Y., Journal of the American Chemical Society 145 (4), 2473-2484 (2023)[2] Swift, M.W., Swift, J.W. & Qi, Y. Modeling the electrical double layer at solid-state electrochemical interfaces. Nat Comput Sci 1, 212–220 (2021)

Diffusion of HTO, 36Cl and 22Na in the Mesozoic rocks of northern Switzerland. II: Data interpretation in terms of an electrical double layer model

It is widely recognised that diffusive transport of charged species in charged clay media must be consistently described for ions with different charge signs and numbers, as well as consistently with pore diffusion schemes for inert solutes that do not undergo interactions with the clay surface. This study presents a modelling approach that meets these requirements for the diffusion of tritiated water, 22Na+ and 36Cl− tracer in heterogeneous Mesozoic sediment sequences of multiple deep-boreholes in northern Switzerland. The model uses an electrical double layer (EDL) approach and a discrete Donnan potential description of cation enrichment and concomitant anion depletion in the Donnan layer close to the basal (planar) clay surfaces to predict effective diffusion coefficients and capacity factors of the charged tracers. It incorporates diffusion data of tritiated water to determine the parameters related to the functional relationships between the accessible porosity and geometry factors with the total clay content as the main input variable. It also calculates concentration enrichment or depletion factors for mobile cationic and anionic species using relationships with the total clay content, such as the average density of surface sites or the thickness of the Donnan layer and the related volume fraction of free pore water. These factors are subsequently used to derive effective diffusion coefficients that include surface diffusion of cations and anion exclusion effects and the related capacity factors. Despite the various lithologies of the rock samples, where significant variability between carbonates and siliciclastic contents are observed, the model shows good agreement with experimental data. Discrepancies between experimental and modelled data are mainly due to inadequacies in the geometric description of diffusion pathways, rather than by potential bias in the calculation of concentration enhancement or depletion factors. However, the model approach assumes that diffusion in clay rock occurs via the pore space of clay minerals and treats all related parameters as simple average values, neglecting heterogeneity of mineral constituents and the unknown statistical distribution of the parameter values.The model has identified the chemical composition of the equilibrium pore water as a significant influencing variable for prediction concentration enhancement or depletion factors and related effective diffusion coefficients. Experimental data obtained for different synthetic pore water compositions support this finding. The robustness of the model predictions across various types of lithologies and formations, all of which exhibit diffusion as the dominant transport mode, is crucial for the generic application of the EDL diffusion model to predict diffusion parameters for elements lacking experimental data.

Direct Experimental Observations of Ion Distributions during Overcharging at the Muscovite-Water Interface by Adsorption of Rb+ and Halides (Cl- , Br- , I- ) at High Salinity.

Classical electric double layer (EDL) models have been widely used to describe ion distributions at charged solid-water interfaces in dilute electrolytes. However, the chemistry of EDLs remains poorly constrained at high ionic strength where ion-ion correlations control non-classical behavior such as overcharging, i. e., the accumulation of counter-ions in amounts exceeding the substrate's surface charge. Here, we provide direct experimental observations of correlated cation and anion distributions adsorbed at the muscovite (001)-aqueous electrolyte interface as a function of dissolved RbBr concentration ([RbBr]=0.01-5.8 M) using resonant anomalous X-ray reflectivity. Our results show alternating cation-anion layers in the EDL when [RbBr]≳100 mM, whose spatial extension (i. e., ~20 Å from the surface) far exceeds the dimension of the classical Stern layer. Comparison to RbCl and RbI electrolytes indicates that these behaviors are sensitive to the choice of co-ion. This new in-depth molecular-scale understanding of the EDL structure during transition from classical to non-classical regimes supports the development of realistic EDL models for technologies operating at high salinity such as water purification applications or modern electrochemical storage.

Electron confinement promoted the electric double layer effect of BiOI/β-Bi2O3 in photocatalytic water splitting

In the realm of photocatalysis, understanding the interface issues (solid/solid and solid/liquid) inherent in heterojunction at the atomic level is the ultimate for engineering an efficient photocatalyst. Herein, an electrophoretic deposition technique is adopted to synthesize BiOI/β-Bi2O3 heterojunction, exhibiting superior photocatalytic activity and stability in H2 evolution (91.5 μmol g–1 h−1) and H2O2 production (11.3 mg L–1 h−1). Combined with the experimental and computational results, a lower free energy of hydrogen evolution reaction (252.4 meV) has been observed contrast to BiOI and β-Bi2O3 samples. A carrier transfer process of like S-scheme heterojunction is proposed based on density of states (DOS) and carrier distribution calculations. The theoretical calculations illustrate the transition dipole moment, migration and accumulation of carrier in BiOI/β-Bi2O3 heterojunction. Subsequent ab initio molecular dynamics (AIMD) results of solid/liquid interface systems (BiOI/β-Bi2O3/H2O and β-Bi2O3/H2O) unravel the interface H2O (solvent) behaviors. The local aggregation of photo-generated electrons in BiOI/β-Bi2O3/H2O leads to a large potential drop, high proton migration rate and the steady electric double layer (EDL) structure compared to the β-Bi2O3/H2O, which facilitates the occurrence of photocatalytic reactions in solution. In addition to offering new insights into the hydrogen evolution and proton transfer in the EDL model and the association between the heterojunction effect and EDL structure, this work also introduces a novel design strategy for Bi-based heterojunctions.

(Invited) Bridging the Gap between the Physics and Chemistry of Electric Double Layer

Classical models of electric double layer (EDL) are mostly concerned with ion distributions and their responses to the surface potential that can be regulated by changing either the voltage or the extent of surface ionization. With the help of adjustable parameters, classical EDL models are able to describe diverse physical phenomena including EDL capacitance and ion transport in good agreement with experimental measurements. However, major challenges remain in understanding chemical reactions within EDL important for the rational design and optimization of electrochemical processes such as energy storage and electrocatalysis. In this talk, I will present a molecular-thermodynamic model to predict the charging behavior of ionizable surfaces under various solution conditions. If a solid is non-conductive, the surface reactions can be reliably described with a Langmuir-type model coupled with liquid-state methods to account for the local thermodynamic non-ideality. When a solid is conductive, however, the electronic properties of different surface sites are intrinsically coupled with each other leading to highly correlated surface reactions. While the brute-force prediction of chemical equilibrium at an electrified surface is computationally prohibitive, a combination of the first-principles calculations and coarse-grained modeling provides complemental information that may be useful for diverse electrochemical applications.

A Dynamic Concentration-Dependent Analytical I,–V Model for LG-GFET Biosensor

In the past few years, liquid-gated graphene field-effect transistors (LG-GFETs) have been widely used in biological detection due to their unique advantages. An accurate transistor model is the basis of biological detection circuit design, however, the reported GFET models are mainly focusing on solid-gated GFETs. Therefore, it is essential to conduct the research on LG-GFET model. In this article, an improved <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\textit{I}$</tex-math> </inline-formula> – <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\textit{V}$</tex-math> </inline-formula> model of LG-GFET is presented based on Fregonese’s model. An improved electric double-layer capacitor model is proposed for LG-GFET. Then, the relationship among iron concentration, bias voltages, and current is studied comprehensively. Furthermore, the drain current response change with time is taken into account and the dynamic concentration-dependent model is established. To verify the accuracy of the proposed model, LG-GFET is simulated in TCAD software and fabricated to perform the measurement. The simulation results and measurement results are compared with the model results, respectively. These results show that the relative root-mean-square error (RMSE) to both simulation and measurement results is less than 5.7%. It is revealed that the proposed model can be applied to biological detection and achieve high accuracy.

Prediction of electrostatic properties of reservoir rock in low salinity water injection into carbonate reservoirs

Geochemical modeling along with chemical reactions is one of the challenges in modeling of low salinity water injection. The most important issue in the geochemical model is to determine the correct electrical charge distribution model and its tuning parameters. The composition of the rock as well as the candidate water used is effective in determining the type of model and its parameters, so that the tuning parameters are determined based on the history of zeta potential experiments. In this study, in order to determine the correct model of electrical charge distribution and its tuning parameters in carbonate rock samples, first, equilibrium samples of Candidate water with crushed rock are subjected to static zeta potential tests. Then, the diffuse electrical double layer model is used to determine the electrical charge of the rock/water and water/oil surfaces and to predict the zeta potential. In the following, by adjusting the tuning parameters of the model to match the prediction results of the model with the history of the laboratory data, the density of the carbonate rock surface, the equilibrium constants and the kinetics of the governing reactions are determined. The obtained results show that the range of error in zeta potential prediction by the model compared to the laboratory data is from 2 to 20%, which is within the acceptable range of the performance of electrical charge distribution models. Moreover, it could be observed that the error of prediction using DLM model is significantly less than the conventional models (CD-MUSIC and BSM) for different candidate water. Finally, the effect of calculated zeta potential changes is used to calculate the contact angle changes of low salinity water injection based on the coupling of DLVO theory and geochemical model. The results of the study prove that the prediction error is less than 5% compared to the results of the static wettability tests. Based on this, according to the good match between the model and the laboratory results, it is possible to determine the properties of surface sites in surface complexation models of carbonate samples using the proposed approach and the subsequent tuning data of the geochemical model.

Electrified interfaces of deep eutectic solvents

Many theoretical and experimental studies have been focused on the physicochemical properties of dense ionic fluids such as ionic liquids (ILs). However, less attention has been given to interfacial properties involving deep eutectic solvents (DES). The impact of the DES composition, hydrogen bond donor (HBD) structure, temperature, and electrode nature material on the DES-electrode vertical interactions remain vague. The lack of knowledge imposes significant constraints in proposing a suitable Electrical Double Layer model (EDL) to describe the DES at electrified interfaces. Measuring differential capacitance-potential curves is a strategy to assess the EDL structure and understand how ions interact with the electrode surface, which knowledge is fundamental to designing and optimizing electrochemical systems for various applications (e.g., energy storage devices). Accordingly, a set of choline chloride-based DESs was assessed containing distinct HBD at their eutectic composition (the polyalcohol's 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, and the amide urea) against glassy carbon (GC), gold (Au), and the platinum (Pt) electrode at different temperatures.The differential capacitance-potential curves were found to vary significantly in shape in the three different electrode surfaces studied, ranging from camel shape (Au electrode), U-shape (GC), and asymmetric bell shape (polycrystalline Pt). The carboxylic malonic and oxalic acids were also assessed for a proper comparison to understand better the role of the HBD's functional group in shaping the electrode-electrolyte structure against the trend found with diol isomers. A suitable EDL model must inevitably accommodate interfacial properties assessed at the capacitive region, namely the influence of the surface chemistry, potential dependence, DES structure molecules, and temperature in shaping the electrified interfacial anatomy.

Design of VN anode catalyst towards enhanced kinetics for vanadium flow batteries

The all-vanadium flow battery (VFB) constantly suffers from sluggish kinetics for the negative electrodes, restricting its operation ability at high current density. To develop an effective catalyst for anode materials, vanadium nitride (VN) is synthesized to decorate the carbon felt (VN-CF). The unique 1-dimension structure and mesoporous character of VN nanorods are beneficial to the mass transfer in the liquid phase. More importantly, by DFT calculation, VN demonstrates strong adsorption energy to the hydrated vanadium ions, thus effectively shortening the distance between reactants and the electrode and accelerating the electron transfer process, which could significantly improve the electrochemical kinetics, from the perspective of the classical electric double layer model theory. As a result, the VN-CF anode exhibits an energy efficiency up to 72.17% at a high current density of 200 mA cm−2, 3.84% higher than the pristine carbon felt electrode. Additionally, the VFB equipped with VN-CF electrode demonstrates superior cycling stability and high-capacity retention. This work provides an innovative idea to uncover the underlying catalytic mechanism of VN, which can also guide the research direction for the high-performance electrocatalyst of VFB in the future.

Liquid-solid contact electrification and its effect on the formation of electric double layer: An atomic-level investigation

Contact electrification at liquid-solid interface has aroused many research interests. Some recent researches suggest that the formation of electric double layer may be dominated by the charge transfer from liquid-solid contact electrification, which challenges the traditional electric double layer models. However, how the liquid-solid contact electrification affects the electrical double layer is still lacking of atomic-level mechanism details. In this work, an atomic-level investigation on the effect of contact electrification on the liquid-solid electric double layer are performed via first-principles and molecular dynamics simulations. The results suggest that the liquid-solid contact electrification can influence the ions distribution in the solution, thus influencing the formation of electric double layer and can even reversing its polarity under specific surface charge density. The mechanism is that the contact charges on the solid surface can affect the adsorption energy of anion/cation at the liquid-solid interface. The conclusion of this work can provide a more comprehensive understanding of the effect of contact electrification to the electric double layer.

Electric Field Effects on Water and Ion Structure and Diffusion at the Orthoclase (001)–Water Interface

Understanding the electrochemical properties of mineral–water interfaces tends to rely upon electrical double layer (EDL) models, but these models are based on the assumption that electrostatic equilibrium is constantly maintained. In reality, interfacial reactions, ion diffusion, and their electrochemical signatures are based in nonequilibrium conditions of locally or globally imbalanced electrical fields where current EDL models have limited purview. Here, we performed molecular dynamics (MD) simulations of the orthoclase (001) surface in contact with a 1 M NaCl aqueous solution under various electric fields, to explore the interplay between EDL structure and dynamics when perturbed by electric fields of different directions and strengths, by confinement, and by different distributions of structural surface charge. The simulations showed that confinement between two opposing (001) surfaces led to the development of an induced field when the applied field was perpendicular to the surfaces and, as a result, to ionic diffusion coefficients that were independent of electric field strength. In contrast, when the applied field was parallel to the surfaces, confinement resulted in ionic diffusion coefficients that were more strongly dependent on the magnitude of the electric field than in bulk water. Differences in the density and distribution of aluminol groups on the two surfaces had a significant impact on how the interfacial structure and dynamics varied in the presence of an electric field. Notably, these differences resulted in an electro-osmotic flow with opposite directions at the two surfaces under parallel applied electric field. Overall, the MD simulations highlighted the importance of considering atomic-level structure and heterogeneities when developing models of the electrochemical properties of mineral–water interfaces.

Comparing Ab Initio Molecular Dynamics and a Semiclassical Grand Canonical Scheme for the Electric Double Layer of the Pt(111)/Water Interface.

The theoretical modeling of metal/water interfaces centers on an appropriate configuration of the electric double layer (EDL) under grand canonical conditions. In principle, ab initio molecular dynamics (AIMD) simulations would be the appropriate choice for treating the competing water-water and water-metal interactions and explicitly considering the atomic and electronic degrees of freedom. However, this approach only allows simulations of relatively small canonical ensembles over a limited period (shorter than 100 ps). On the other hand, computationally efficient semiclassical approaches can treat the EDL model based on a grand canonical scheme by averaging the microscopic details. Thus, an improved description of the EDL can be obtained by combining AIMD simulations and semiclassical methods based on a grand canonical scheme. By taking the Pt(111)/water interface as an example, we compare these approaches in terms of the electric field, water configuration, and double-layer capacitance. Furthermore, we discuss how the combined merits of the approaches can contribute to advances in EDL theory.

Amorphous alumina supercapacitors with voltage-charging performance

The electric storage effect of fast charging by voltage application for amorphous alumina (cAAO) supercapacitors fabricated using a crystalline aluminum alloy was investigated in terms of charging/discharging behaviors and AC impedance. The mechanism for the electrical storage of a cAAO supercapacitor was proposed based on the coupling of electrons on Al atoms and positively charged holes in Al vacancies, using an electric double-layer model containing an electrolyte with an electrical resistivity of 6.3 × 105Ωcm. The supercapacitor demonstrated fast charging at a voltage application of up to 500 V.

Modeling salt adsorption in electrical double layer for capacitive deionization

AbstractThis work presents an electrical double layer (EDL) model for capacitive deionization (CDI) by intercorrelating the salt adsorption, the electrode voltage, and the surface charge density. The counterion condensation is considered a crucial contribution to salt adsorption because of the high surface charge density in the charged micropores. The counterions condense when the surface charge density exceeds a critical value, which is predicted by the counterion condensation theory. The EDL model accurately correlates the NaCl salt adsorption and electrode voltage with various surface charge densities and well predicts the salt adsorption in a wide range of external salt concentrations. The EDL model reproduces the non‐monotonic relationship between the salt adsorption and the specific surface area observed in experiments and provides an explanation from the modeling perspective. Exhibiting superior accuracy and predictability for salt adsorption, the EDL model could serve as an enabling tool contributing to the development of CDI processes.

A review of transport models in charged porous electrodes

There is increased interest in many different processes based upon interactions between a charged solid surface and a liquid electrolyte. Energy storage in capacitive porous materials, ionic membranes, capacitive deionization (CDI) for water desalination, capacitive energy generation, removal of heavy ions from wastewater streams, and geophysical applications are some examples of these processes. Process development is driven by the production of porous materials with increasing surface area. Understanding of the physical phenomena occurring at the charged solid-electrolyte interface will significantly improve the design and development of more effective applied processes. The goal of this work is to critically review the current knowledge in the field. The focus is on concepts behind different models. We start by briefly presenting the classical electrical double layer (EDL) models in flat surfaces. Then, we discuss models for porous materials containing macro-, meso-, and micro-pores. Some of the current models for systems comprising two different pore sizes are also included. Finally, we discuss the concepts behind the most common models used for ionic transport and Faradaic processes in porous media. The latter models are used for simulation of electrosorption processes in porous media.

Gating ion and fluid transport with chiral solvent.

The development of modern membranes for ionic separations and energy-storage devices such as supercapacitors depends on the description of ions at solid interfaces, as is often provided by the electrical double layer (EDL) model. The classical EDL model ignores, however, important factors such as possible spatial organization of solvent at the interface and the influence of the solvent on the spatial dependence of the electrochemical potential; these effects in turn govern electrokinetic phenomena. Here we provide a molecular-level understanding of how solvent structure can dictate ionic distributions at interfaces using a model system of a polar, aprotic solvent, propylene carbonate, in its enantiomerically pure and racemic forms, at a silica interface. We link the interfacial structure to the tuning of ionic and fluid transport by the chirality of the solvent and the salt concentration. The results of nonlinear spectroscopic experiments and electrochemical measurements suggest that the solvent exhibits lipid-bilayer-like interfacial organization, with a structure that is dependent on the solvent chirality. The racemic form creates highly ordered layered structure that dictates local ionic concentrations, such that the effective surface potential becomes positive in a wide range of electrolyte concentrations. The enantiomerically pure form exhibits weaker ordering at the silica surface, which leads to a lower effective surface charge induced by ions partitioning into the layered structure. The surface charge in silicon nitride and polymer pores is probed through the direction of electroosmosis that the surface charges induce. Our findings add a new dimension to the nascent field of chiral electrochemistry, and emphasize the importance of including solvent molecules in descriptions of solid-liquid interfaces.

Origin and predictive principle for selective products of electrocatalytic carbon dioxide reduction

A computational method, based on DFT and electrical double-layer interface models with explicit hydrogen bonding, is developed to accurately predict potential-dependent reaction pathways, catalytic activity, and product selectivity of CO2 reduction.