Structure Of Electrical Double Layer Research Articles

Effect of solvent on electric double layer capacitance and over screening inside spherical cavity by density functional theory

In this article, the solvent primitive model (SPM) and the restricted primitive model (RPM) in the framework of modified fundamental measure theory are compared for the prediction of the electric double layer (EDL) at the contact surface of the concave wall of a charged spherical cavity. The structure of EDL, EDL capacitance, Stern and diffuse contributions, zeta potential, and over screening phenomenon are predicted and compared with the two models. Our results show that considering the solvent molecules as hard spheres according to SPM leads to an appearance of layering structure and oscillatory behavior of density profiles inside the cavity. Also, the amount of ion adsorption in SPM is greater than that of RPM at the same condition. As a result of more counter-ion adsorption in comparison to co-ion adsorption, the total net charge inside the cavity increases. That way, the predicted amount of EDL capacitance and its diffuse contribution by SPM are greater than the corresponding values by RPM. Note that the Stern contribution to the capacitance has the same value in both models at fixed and equal sizes of ions and solvent molecules. Finally, the mean electrostatic potential (MEP) in the cavity, which is strongly affected by more counter-ion adsorption in SPM, shows evidence of an over screening phenomenon in the stern region at a lower concentration in comparison to RPM. Also, the slope of MEP is higher for SPM (in the Stern region), which leads to lower absolute values for its zeta potential.

Magnetic supercapacitors: Charge storage mechanisms, magnetocapacitance, and magnetoelectric phenomena

Pseudocapacitive (PC) materials are under investigation for energy storage in supercapacitors, which exhibit exceptionally high capacitance, good cyclic stability, and high power density. The ability to combine high electrical capacitance with advanced ferrimagnetic or ferromagnetic properties in a single material at room temperature opens an avenue for the development of advanced magnetically ordered pseudocapacitive (MOPC) materials. This review covers materials science aspects, charge storage mechanisms, magnetocapacitance, and magnetoelectric (ME) phenomena in MOPC materials. Recent studies demonstrate high PC properties of advanced ferrimagnetic materials, such as spinel ferrites and hexagonal ferrites. Of particular importance is the discovery of PC properties of perovskite-type manganites, which exhibit room temperature ferromagnetism and giant negative magnetoresistance. The coupling of high capacitance and magnetization in MOPC provides a platform for strong ME interactions. Various strategies are used for manipulation of electrical capacitance/magnetization of MOPC by a magnetic field/electrode potential. Magnetocapacitance studies show significant increase in capacitance of MOPC under the influence of a magnetic field. Moreover, the application of a magnetic field results in enhanced energy density and power density, reduction of resistance, and improvement of cyclic stability. Such findings offer a potential of a breakthrough in the development of advanced supercapacitors. High magnetocapacitance and ME phenomena are linked to the influence of magnetic fields on electrolyte diffusion, structure of electrical double layer, charge transfer resistance, and variation of conductivity and magnetization of MOPC materials, which facilitate charge/discharge behavior. Various applications of ME effect in MOPC are discussed. Moreover, advantages of magnetocapacitive MOPC are described for applications in electronic and spintronic devices, supercapacitors, and devices for magnetically enhanced capacitive deionization of water.

Molecular scale roughness effects on electric double layer structure in asymmetric ionic liquids

Molecular scale roughness effects on electric double layer structure in asymmetric ionic liquids

A Gaussian field approach to the planar electric double layer structures in electrolyte solutions.

In this work, the planar, electric, double-layer structures of non-polarizable electrodes in electrolyte solutions are studied with Gaussian field theory. A response function with two Yukawa functions is used to capture the electrostatic response of the electrolyte solution, from which the modified response function in the planar symmetry is derived analytically. The modified response function is further used to evaluate the induced charge density and the electrostatic potential near an electrode. The Gaussian field theory, combined with a two-Yukawa response function, can reproduce the oscillatory decay behavior of the electric potentials in concentrated electrolyte solutions. When the exact sum rules for the bulk electrolyte solutions and the electric double layers are used as constraints to determine the parameters of the response function, the Gaussian field theory could at least partly capture the nonlinear response effect of the surface charge density. Comparison with results for a planar electrode with fixed surface charge densities from molecular simulations demonstrates the validity of Gaussian field theory.

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.

Development of Mesoporous Carbon Composites with Waste Plastics Derived Graphene and MnO2 for Supercapacitor Applications

This study demonstrates the influence of incorporating the composites such as waste plastics derived graphene (WPDG) and manganese dioxide (MnO2) in the mesoporous carbon (CR) and their consequent characteristics. The CR having WPDG as composite is named as CRG and MnO2 containing CR composite is termed as CRM. CRG possess the surface area as high as 790 m2g−1 along with pore volume of 0.565 cc g−1 and radius of 3.82 nm. Cyclic voltammetry (CV) study suggested that CR and CRG showed non-Faradic capacitive behavior with almost rectangular shaped CV profiles at low scan rates and this shows the existence of electric double layer structure. On the other hand, pseudo-capacitance is observed for CRM. Galvanostatic charge/discharge investigation revealed that the specific capacitance can be enhanced by 6 times upon subsequent immobilization of WPDG in CR whereas 4-fold upgrading in the specific capacitance after treating CR with MnO2. Interestingly, CRM showed higher capacitance retention as compared to CRG and is attributed to its smaller value of equivalent series resistance as compared to CRG. Ragone plots shown that the higher energy and power densities are found for the case of CRG.

Molecular insights into the electric double-layer structure at a polymer electrolyte-electrode interface

Polymer electrolyte-based electric double-layer supercapacitors (EDLCs) have been increasingly studied for flexible, wearable, and multifunctional energy storage applications. Although the phenomenon that electrode materials present significantly lower EDL capacitances in polymer electrolytes than in liquid electrolytes has been widely observed, it has not been well studied and explained. Here we present the molecular dynamics simulation of a representative polymer electrolyte-based EDLC to reveal the atomic structure of such a polymer electrolyte-electrode interface for the first time. The polymer electrolyte composed of polyethylene oxide and lithium perchlorate is simulated between graphene electrodes and compared with an aqueous electrolyte-based system with the same lithium salt. We find that the polymer-based system shows unique EDL structures in the inner and outer Helmholtz layers that are not seen in the aqueous one. Statistical analyses along with ab initio calculations show that the disparities mainly come from the different interaction strengths between ions, polymer or water molecules, and graphene electrodes. Despite these disparities, the intrinsic interfacial capacitances calculated from various simulated charge states of different EDLCs show very close values. Combined with experimental measurements, we conclude that the reduced capacitances with polymer electrolytes reported in the literature come from the poor interface between electrode and electrolyte, which can be significantly improved through proper thermal treatments.

Size Effect of Electrolyte Ions on the Electric Double-Layer Structure and Supercapacitive Behavior

Finding a viable electrolyte for next-generation supercapacitors is of primary importance for developing supercapacitors with high power and energy densities. Herein, we synthesized a conducting salt, tetramethylphosphonium tetrafluoroborate (TMPBF4), and compared the electrochemical characteristics of supercapacitor devices containing TMPBF4 or 1,1-dimethylpyrrolidinium tetrafluoroborate (DMPBF4). The TMPBF4 salt was selected based on the generally accepted design rule that smaller ions and solvation shells contribute to higher energy and power densities. However, at a low current density (0.1 A g–1), supercapacitors with TMPBF4 in acetonitrile (AN) exhibited a slightly lower capacitance (24.6 ± 0.1 F g–1) than those with DMPBF4 (25.0 ± 0.2 F g–1). Clarification of this behavior using electrochemical and theoretical methods revealed that the total capacitance is influenced by not only the size of the ions but also the degree of cation–anion interactions near the electrodes. By contrast, at a high current density of 10 A g–1, supercapacitors with TMPBF4 showed an 18% increase in capacitance relative to those with DMPBF4. Supercapacitors with TMPBF4 exhibited both high capacitance and a remarkably long cycle life (10,000 cycles) at a high working voltage (3.2 V) and high current density (10 A g–1). Furthermore, supercapacitors utilizing TMPBF4/AN provided a sufficiently fast frequency response for 60 Hz alternating current (ac) line filtering. These insights into the influence of the investigated electrolyte salts on the formation of electric double-layer structures offer design rules for developing electrolytes for supercapacitors.

Molecular understanding of the Helmholtz capacitance difference between Cu(100) and graphene electrodes.

Unraveling the origin of Helmholtz capacitance is of paramount importance for understanding the interfacial structure and electrostatic potential distribution of electric double layers (EDL). In this work, we combined the methods of ab initio molecular dynamics and classical molecular dynamics and modeled electrified Cu(100)/electrolyte and graphene/electrolyte interfaces for comparison. It was proposed that the Helmholtz capacitance is composed of three parts connected in series: the usual solvent capacitance, water chemisorption induced capacitance, and Pauling repulsion caused gap capacitance. We found the Helmholtz capacitance of graphene is significantly lower than that of Cu(100), which was attributed to two intrinsic factors. One is that graphene has a wider gap layer at interface, and the other is that graphene is less active for water chemisorption. Finally, based on our findings, we provide suggestions for how to increase the EDL capacitance of graphene-based materials in future work, and we also suggest that the new understanding of the potential distribution across the Helmholtz layer may help explain some experimental phenomena of electrocatalysis.

Non-polar ether-based electrolyte solutions for stable high-voltage non-aqueous lithium metal batteries

The electrochemical instability of ether-based electrolyte solutions hinders their practical applications in high-voltage Li metal batteries. To circumvent this issue, here, we propose a dilution strategy to lose the Li+/solvent interaction and use the dilute non-aqueous electrolyte solution in high-voltage lithium metal batteries. We demonstrate that in a non-polar dipropyl ether (DPE)-based electrolyte solution with lithium bis(fluorosulfonyl) imide salt, the decomposition order of solvated species can be adjusted to promote the Li+/salt-derived anion clusters decomposition over free ether solvent molecules. This selective mechanism favors the formation of a robust cathode electrolyte interphase (CEI) and a solvent-deficient electric double-layer structure at the positive electrode interface. When the DPE-based electrolyte is tested in combination with a Li metal negative electrode (50 μm thick) and a LiNi0.8Co0.1Mn0.1O2-based positive electrode (3.3 mAh/cm2) in pouch cell configuration at 25 °C, a specific discharge capacity retention of about 74% after 150 cycles (0.33 and 1 mA/cm2 charge and discharge, respectively) is obtained.

Correction to “Electrical Double Layer Structure in Ionic Liquids and Its Importance for Supercapacitor, Battery, Sensing, and Lubrication Applications”

Correction to “Electrical Double Layer Structure in Ionic Liquids and Its Importance for Supercapacitor, Battery, Sensing, and Lubrication Applications”

Molecular Dynamics Simulation of the Interfacial Structure and Differential Capacitance of [BMI+][PF6−] Ionic Liquids on MoS2 Electrode

MoS2 nanomaterials and ionic liquids (ILs) have attracted tremendous interest as the prime electrodes and electrolytes of supercapacitors. However, the corresponding charge storage mechanisms have not yet been clearly understood. Herein, we study the molecular-level energy storage mechanisms of the MoS2 electrode in imidazolium ionic liquid ([BMI+][PF6−]) using molecular dynamics (MD) simulation. The electric double-layer (EDL) structures of MoS2 electrodes in [BMI+][PF6−] electrolytes are comprehensively studied in terms of number density, MD snapshots, separation coefficient, and ion-electrode interaction energy. Based on this, the electric potential and electric field distributions are calculated by integrating Poisson equations. Importantly, a bell-shaped differential capacitance profile is proposed, different from the U-shaped curve from the conventional Gouy–Chapman theory. Especially, it can be well reproduced by the differential charge density curve in the Helmholtz layer. This indicates that the capacitive behaviors of the MoS2 electrode are primarily determined by the counterion population/structure in the EDL region 5.0 Å from the electrode surface. In the end, ion diffusion coefficients within different interfacial EDL regions are evaluated, revealing that dynamics are significantly suppressed by ~50% in the Helmholtz region. However, the dynamics can be recovered to a bulk state with the ion position 10 Å away from the electrode surface. The as-obtained insights reveal the charge storage mechanisms of MoS2 in ILs, which can provide useful guidance on improving the energy density of MoS2 supercapacitors.

Effect of the Electric Double Layer (EDL) in Multicomponent Electrolyte Reduction and Solid Electrolyte Interphase (SEI) Formation in Lithium Batteries.

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. In this work, a newly developed model was used to 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. Both electrolytes have fluoroethylene carbonate (FEC) as a common additive to form the beneficial F-containing SEI component (e.g., LiF). However, the role of FEC drastically differs in these electrolytes. FEC is an effective SEI modifier for the carbonate-based electrolyte by being the only F-containing species entering the EDL and being reduced, as the anion (PF6-) will not enter the EDL. For the ether-based electrolyte, both the anion (TFSI-) and FEC can enter the EDL and be reduced. The competition of the two species within the EDL due to the surface charge and temperature leads to a unique temperature effect observed in prior experiments: the FEC additive is more effective in modulating SEI components at a low temperature (-40 °C) than at room temperature (20 °C) in the ether-based electrolyte. These collective quantitative agreements with experiments emphasize the importance of incorporating the effect of the EDL in multicomponent electrolyte reduction reactions in simulations/experiments to predict/control the formation of the SEI layer.

Simulation of the cyclic voltammetric response of an outer-sphere redox species with inclusion of electrical double layer structure and ohmic potential drop.

A finite-element model has been developed to simulate the cyclic voltammetric (CV) response of a planar electrode for a 1e outer-sphere redox process, which fully accounts for cell electrostatics, including ohmic potential drop, ion migration, and the structure of the potential-dependent electric double layer. Both reversible and quasi-reversible redox reactions are treated. The simulations compute the time-dependent electric potential and ion distributions across the entire cell during a voltammetric scan. In this way, it is possible to obtain the interdependent faradaic and non-faradaic contributions to a CV and rigorously include all effects of the electric potential distribution on the rate of electron transfer and the local concentrations of the redox species Oz and Rz-1. Importantly, we demonstrate that the driving force for electron transfer can be different to the applied potential when electrostatic interactions are included. We also show that the concentrations of Oz and Rz-1 at the plane of electron transfer (PET) significantly depart from those predicted by the Nernst equation, even when the system is characterised by fast electron transfer/diffusion control. A mechanistic rationalisation is also presented as to why the electric double layer has a negligible effect on the CV response of such reversible systems. In contrast, for quasi-reversible electron transfer the concentrations of redox species at the PET are shown to play an important role in determining CV wave shape, an effect also dependant on the charge of the redox species and the formal electrode potential of the redox couple. Failure to consider electrostatic effects could lead to incorrect interpretation of electron-transfer kinetics from the CV response. Simulated CVs at scan rates between 0.1 and 1000 V s-1 are found to be in good agreement with experimental data for the reduction of 1.0 mM Ru(NH3)63+ at a 2 mm diameter gold disk electrode in 1.0 M potassium nitrate.

Evolution of the electrical double layer with electrolyte concentration probed by second harmonic scattering.

Investigating the electrical double layer (EDL) structure has been a long-standing challenge and has seen the emergence of several sophisticated techniques able to probe selectively the few molecular layers of a solid/water interface. While a qualitative estimation of the thickness of the EDL can be obtained using simple theoretical models, following experimentally its evolution is not straightforward and can be even more complicated in nano- or microscale systems, particularly when changing the ionic concentration by several orders of magnitude. Here, we bring insight into the structure of the EDL of SiO2 nanoparticle suspensions and its evolution with increasing ionic concentration using angle-resolved second harmonic scattering (AR-SHS). Below millimolar salt concentrations, we can successively characterize inner-sphere adsorption, diffuse layer formation, and outer-sphere adsorption. Moreover, we show for the first time that, by appropriately selecting the nanoparticle size, it is possible to retrieve information also in the millimolar range. There, we observe a decrease in the magnitude of the surface potential corresponding to a compression in the EDL thickness, which agrees with the results of several other electroanalytical and optical techniques. Molecular dynamics simulations suggest that the EDL compression mainly results from the diffuse layer compression rather than outer-sphere ions (Stern plane) moving closer to the surface.

From energy storage to pathogen eradication: unveiling the antibacterial and antiviral capacities of flexible solid-state carbon cloth supercapacitors.

With the emergence of deadly viral and bacterial infections, preventing the spread of microorganisms on surfaces has gained ever-increasing importance. This study investigates the potential of solid-state supercapacitors as antibacterial and antiviral devices. We developed a low-cost and flexible carbon cloth supercapacitor (CCSC) with highly efficient antibacterial and antiviral surface properties. The CCSC comprised two parallel layers of carbon cloth (CC) electrodes assembled in a symmetric, electrical double-layer supercapacitor structure that can be charged at low potentials between 1 to 2 V. The optimized CCSC exhibited a capacitance of 4.15 ± 0.3 mF cm-2 at a scan rate of 100 mV s-1, high-rate capability (83% retention of capacitance at 100 mV s-1 compared to its value at 5 mV s-1), and excellent electrochemical stability (97% retention of the initial capacitance after 1000 cycles). Moreover, the CCSC demonstrated outstanding flexibility and retained its full capacitance even when bent at high angles, making it suitable for wearable or flexible devices. Using its stored electrical charge, the charged CCSC disinfects bacteria effectively and neutralizes viruses upon surface contact with the positive and negative electrodes. The charged CCSC device yielded a 6-log CFU reduction of Escherichia coli bacterial inocula and a 5-log PFU reduction of HSV-1 herpes virus. Antibacterial and antiviral carbon cloth supercapacitors represent a promising platform technology for various applications, including electronic textiles and electronic skins, health monitoring or motion sensors, wound dressings, personal protective equipment (e.g., masks) and air filtration systems.

Directing oxygen reduction reaction selectivity towards hydrogen peroxide via electric double layer engineering.

The electrochemical oxygen reduction reaction (ORR) has been recognized as a promising alternative for the sustainable production of H2O2. Here, we report a facile and effective strategy to promote ORR selectivity towards the 2e- product H2O2via electric double layer engineering. Specifically, in a model system using immobilized cobalt phthalocyanine as the electrocatalyst, H2O2 selectivity has been improved from below 60% to over 93%, and the intrinsic activity for H2O2 formation has been enhanced by more than 3 times upon the introduction of a cationic surfactant (i.e., cetyltrimethylammonium bromide, CTAB) into the electrolyte. Based on detailed kinetics analysis, we conclude that the accelerated H2O2 formation rate results from the reduced charge transfer resistance in the rate limiting step and the promoted oxygen uptake rate. We propose that the electric field strength across the electric double layer is enhanced via the self-assembled single-tail cationic surfactant layer at the electrode/electrolyte interface, which is the origin of the enhancement of the 2e- ORR performance.

Incorporating ion-specific van der Waals and soft repulsive interactions in the Poisson-Boltzmann theory of electrical double layers.

Electrical double layers (EDLs) arise when an electrolyte is in contact with a charged surface, and are encountered in several application areas including batteries, supercapacitors, electrocatalytic reactors, and colloids. Over the last century, the development of Poisson-Boltzmann (PB) models and their modified versions have provided significant physical insight into the structure and dynamics of the EDL. Incorporation of physics such as finite-ion-size effects, dielectric decrement, and ion-ion correlations has made such models increasingly accurate when compared to more computationally expensive approaches such as molecular simulations and classical density functional theory. However, a prominent knowledge gap has been the exclusion of van der Waals (vdW) and soft repulsive interactions in modified PB models. Although short-ranged as compared to electrostatic interactions, we show here that vdW and soft repulsive interactions can play an important role in determining the structure of the EDL via the formation of a Stern layer and in modulating the differential capacitance of an electrode in an electrolyte. To this end, we incorporate ion-ion and wall-ion vdW attraction and soft repulsion via a 12-6 Lennard-Jones (LJ) potential, resulting in a modified PB-LJ approach. The wall-ion LJ interactions were found to have a significant effect on the electrical potential and concentration profiles, especially close to the wall. However, ion-ion LJ interactions do not affect the EDL structure at low bulk ion concentrations (<1 M). We also derive dimensionless numbers to quantify the impact of ion-ion and wall-ion LJ interactions on the EDL. Furthermore, in the pursuit of capturing ion-specific effects, we apply our model by considering various ions such as Na, K+, Mg2+, Cl-, and SO42-. We observe how varying parameters such as the electrolyte concentration and electrode potential affect the structure of the EDL due to the competition between ion-specific LJ and electrostatic interactions. Lastly, we show that the inclusion of vdW and soft repulsion interactions, as well as hydration effects, leads to a better qualitative agreement of the PB models with experimental double-layer differential capacitance data. Overall, the modified PB-LJ approach presented herein will lead to more accurate theoretical descriptions of EDLs in various application areas.

Molecular Insights into Curvature Effects on the Capacitance of Electrical Double Layers in Tricationic Ionic Liquids with Carbon Nanotube Electrodes.

Ionic liquid (IL) electrolytes and carbon nanotube (CNT) electrodes have exhibited promising electrochemical performance in supercapacitors. Nevertheless, the adaptability of tricationic ILs (TILs) in CNT-based supercapacitors remains unknown. Herein, the performance of supercapacitors with (6,6), (8,8), (12,12), and (15,15) CNT electrodes in the TIL [C6(mim)3](Tf2N)3 was assessed via molecular dynamics simulations, paying attention to the electric double-layer (EDL) structures and the relations between the CNT curvature and capacitance. The results disclose that counterion and co-ion number densities near CNT electrodes have a marked reduction, compared with that of the graphene electrode. The capacitance of the EDL in the TIL increases significantly as the CNT curvature increases and the capacitance of the TIL/CNT systems is higher than that of the TIL/graphene system. Moreover, different EDL structures in the TIL and the monocationic IL (MIL) [C6mim][Tf2N] near CNT electrodes were revealed, showing higher-concentration anions [Tf2N]- at the CNT surfaces in the TIL. It is also verified that the TIL has a greater energy-storage ability under high potentials. Furthermore, the almost flat or weakly camel-like capacitance-voltage (C-V) curve of EDLs in the TIL turns into a bell shape in the MIL, because of the ion accumulation at the CNT surfaces and the associations between ions.

Electric Double Layer Structure in Electrocatalytic Carbon Dioxide Reduction

Environmental degradation and climate change caused by excessive CO2 emissions have become the most serious challenges facing humanity. The electrocatalytic CO2 reduction reaction (CO2RR) is an ideal way to produce high‐value chemicals and solve environmental pollution at the same time. The electric double layer (EDL) structure at the electrochemical interface can greatly influence the local catalytic environment, but it is not fully understood. Herein, recent advances in EDL structure for CO2RR are focused. The main components of the EDL, including adsorbates on the electrode surface, metal/water interface, cations, anions, and differential capacitance are described. The latest experimental and theoretical understanding of EDL and their impact on CO2RR are presented. Finally, the current challenges encountered and the outlook for future development are discussed. This review describes the influence of EDL structure on CO2 reduction, which is of guiding significance for the design of new and efficient CO2 electrocatalysts.