Structure Of Electrical Double Layer Research Articles

EIS and relaxation times analysis of the electric double layer construction on Pt cathode surface in MgCl2 molten salt hydrate

The electric double layer on Pt cathode surface in the process of cathodic polarization was analyzed with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), Raman spectroscopy, and Scanning electron microscope (SEM) in magnesium chloride (MgCl2) solution and MgCl2 molten salt hydrate (MSH). The effects of KCl on the structure of MgCl2 molten salt hydrate and electrode reaction were discussed. EIS data were fitted to propose the equivalent electric circuits to simulate the structure of electric double layers on Pt electrodes. Distribution of relaxation times (DRT) analysis was estimated to identify each process for MgCl2 solution and MgCl2 molten salt hydrate on the Pt cathode. The results show that the solution transforms into MSHs as the water content in the solution decreases. The solution and molten salt exhibit different double-layer properties. The movement of hydrated ions has greater resistance in MSHs which leads to the reduction of electrode reaction rate. The DRT and EIS results demonstrate that H+ and hydrated Mg2+ are simultaneously adsorbed on the Pt surface to form a double electric layer in MgCl2 solution or MSHs. In the MgCl2 MSHs, H+, H2O, and compact hydrated Mg2+ on the Pt electrode surface form a double layer. KCl plays an important role in changing the structure of MgCl2 molten salt hydrate, increasing the active H2O, and offering H+ adsorbed on the Pt surface.

In-plane structure of the electric double layer in the primitive model using classical density functional theory.

The electric double layer (EDL) has a pivotal role in screening charges on surfaces as in supercapacitor electrodes or colloidal and polymer solutions. Its structure is determined by correlations between the finite-sized ionic charge carriers of the underlying electrolyte, and, this way, these correlations affect the properties of the EDL and of applications utilizing EDLs. We study the structure of EDLs within classical density functional theory (DFT) in order to uncover whether a structural transition in the first layer of the EDL that is driven by changes in the surface potential depends on specific particle interactions or has a general footing. This transition has been found in full-atom simulations. Thus far, investigating the in-plane structure of the EDL for the primitive model (PM) using DFT has proved a challenge. We show here that the use of an appropriate functional predicts the in-plane structure of EDLs in excellent agreement with molecular dynamics simulations. This provides the playground to investigate how the structure factor within a layer parallel to a charged surface changes as a function of both the applied surface potential and its separation from the surface. We discuss pitfalls in properly defining an in-plane structure factor and fully map out the structure of the EDL within the PM for a wide range of electrostatic electrode potentials. However, we do not find any signature of a structural crossover and conclude that the previously reported effect is not fundamental but rather occurs due to the specific force field of ions used in the simulations.

Al and Mn speciation changes during the pre-oxidation with potassium permanganate and coagulation removing natural organic matter and its membrane fouling behavior

In this study, we systematically explore coagulation behavior, ultrafiltration membrane fouling behavior and the mechanism involved in during the process of pre-oxidation of potassium permanganate and coagulation of aluminum chloride at different condition to treat model pollutants (humic acid, HA) and natural water. The KMnO4 pre-oxidation significantly enhances flocs formation, and for HA artificial water the flocs size increases from 82 to 122 μm at pH 5.5, from 63 to 185 μm at pH 7.0 and from 0 to 75 μm at pH 8.5, respectively, as for natural water it increases from 72 to 139 μm. The enhanced coagulation at pH 5.5 is attributed to the increased polymeric Al speciation after pre-oxidation along with the generated Mn2+ damaging the electric double layer structure. And for pH 8.5 it is mainly caused by the in-situ MnO2 as combination nuclei during pre-oxidation. Besides, for pH 7.0, the combined effect of in-situ MnO2 and the increased polymeric Al speciation both contribute to improvement of the coagulation. What's more, the enhanced Al coagulation by pre-oxidation of KMnO4 also helps alleviate the membrane fouling for both HA artificial water and natural water, and a much rougher surface with larger flocs forms after KMnO4-aided Al coagulation filtration. This study provides an alternative perspective on the mechanism of pre-oxidation coagulation process.

Second harmonic generation as a probe of structure and dynamics of ionic liquids at the electrode interface

Electrochemical second harmonic generation (ESHG) has been applied as a probe of the slow dynamics in the electric double layer (EDL) at the ionic liquid (IL)/Au interface. When the electrode potential was stepped, the SHG signal from the interface was relaxed on the time scale longer than tens of seconds, which is distinctively slower than the RC time constant of the cell. This ultraslow relaxation in ESHG was quantitatively analyzed and discussed for several ILs, revealing that the ultraslow relaxation itself is a common phenomenon for the EDL in the ILs studied but the asymmetry of the time constants to the potential-step directions depends on the IL ions, which is likely to reflect the structure ordering of the interfacial ionic layer in the EDL depending on both ILs and the potential. The EDL structure in equilibrium has also been investigated via SHG measurements with a potential scan at a sufficiently slow rate; the potential dependence of the SHG signal was found to deviate from a simple parabolic one, reflecting the camel-shaped static differential capacitance for the EDL in ILs.

Theoretical Insight into the Imidazolium-Based Ionic Liquid Interface Structure and Differential Capacitance on Au(111): Effects of the Cationic Substituent Group.

Electric double layers (EDLs) play a key role in the electrochemical and energy storage of supercapacitors. It is important to understand the structure and properties of EDLs. In this work, quantum chemical calculations and molecular dynamics (MD) simulations are used to study the microstructure of EDLs of four different substituents of imidazolium-based bis(trifluoromethylsulfonyl)imide ionic liquids (ILs) on the Au(111) surface. It is shown that the particle interactions influence the different arrangements of the anion and cation. More alkyl substitutions and longer alkyl chains result in a higher ELUMO and thus a stronger interaction energy between cations and electrodes. Strong interactions produce linear patterns of anions/cations on the electrode and a maximum value of differential capacitance near PZC, whereas weak interactions generate worm-like patterns of anions/cations on Au(111) and a minimum value of differential capacitance near the PZC. We hold the opinion that the alkyl substitution has more effects on the EDLs. Our analysis provides a new perspective on EDLs structures at the atomic and molecular level. This study provides a good basis and guidance for further understanding the interface phenomena and characteristics of ionic liquids in electrochemical and energy device applications.

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.

Electric Double Layer Effects in Electrocatalysis: Insights from Ab Initio Simulation and Hierarchical Continuum Modeling.

Structures of the electric double layer (EDL) at electrocatalytic interfaces, which are modulated by the material properties, the electrolyte characteristics (e.g., the pH, the types and concentrations of ions), and the electrode potential, play crucial roles in the reaction kinetics. Understanding the EDL effects in electrocatalysis has attracted substantial research interest in recent years. However, the intrinsic relationships between the specific EDL structures and electrocatalytic kinetics remain poorly understood, especially on the atomic scale. In this Perspective, we briefly review the recent advances in deciphering the EDL effects mainly in hydrogen and oxygen electrocatalysis through a multiscale approach, spanning from the atomistic scale simulated by ab initio methods to the macroscale by a hierarchical approach. We highlight the importance of resolving the local reaction environment, especially the local hydrogen bond network, in understanding EDL effects. Finally, some of the remaining challenges are outlined, and an outlook for future developments in these exciting frontiers is provided.

Hybrid electrolyte engineering enables reversible Zn metal anodes at ultralow current densities

Parasitic reactions in aqueous Zn metal batteries tend to be intensified along with the decrease of current density, deteriorating the cycling stability of Zn anodes, which unfortunately have been overlooked in previous studies. Herein, an organic solvent N-Methylacetamide (NMA) is introduced into ZnSO4 electrolyte for improving the reversibility of Zn anodes. Combined with theoretical and experimental investigations, it is uncovered that NMA additives are capable of entering not only the pristine Zn2+ solvation structure ([Zn(H2O)x]2+) but also the electrical double layer structure, reducing active H2O molecule proportions and thus suppressing the corrosion reactions. Meanwhile, nucleation and growth processes are also constrained with NMA additive for its strong coordination with Zn2+, inducing dendrite-free Zn depositions. Consequently, an average Coulombic efficiency (CE) of 98.5% for 600 cycles in Zn|Cu half-cells with NMA/ZnSO4 electrolyte is obtained at an ultralow current density of 0.3 mA cm−2. Moreover, Zn|Zn symmetric cells utilizing 20 vol% NMA additive exhibit stable cycle lifespan of 1000 h. Benefitting from the enhanced reversibility of Zn anodes in NMA/ZnSO4 electrolytes, full-cells assembled with carbon cloth as cathodes deliver high performance of 5200 cycles at the current density of 64 mA g−1 with 10 μm thin Zn anodes, favoring the practical applications.

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) Modeling of the Bulk and Electrical Double-Layer Structures of Localized High-Concentration Electrolytes

A new class of electrolytes, localized high-concentration electrolytes (LHCE), have shown many benefits to high-capacity electrodes (lithium (Li)-metal, silicon, sodium, zinc, and potassium).[1] These electrolytes combine high-concentration electrolytes (HCE) with salt and solvent with low-viscosity diluents. The dilutes were added to increase ionic conductivity while the locally highly concentrated salt-solvent clusters will facilitate stable solid-electrolyte interphase (SEI) formation while preventing metallic-dendrite formation. For example, it was demonstrated that an LHCE based on lithium bis(fluorosulfonyl)imide (LiFSI) salt, Dimethoxyethane (DME) solvent, and tris(2,2,2-trifluoroethyl)orthoformate (TFEO) diluent (e.g., LiFSI-1.2DME-2TFEO by mol) forms inorganic-rich, monolithic SEI and shows excellent cycling performance for Li-metal batteries under practical conditions.[2] Here, the interactions among cations, anions, solvent molecules, and diluent molecules create a complex design space, making the trial-and-error empirical approach less efficient.Using density functional theory and classical molecular dynamics simulations, we reveal several important design principles:a) The dielectric constant of the pure solvent or diluent is not a good descriptor to describe the solubility of the salt in solvent and diluent.b) The single ion–solvent (diluent) binding energy is insufficient to predict the solubility, which also depends on the molecular structures and the corresponding solvation shell structure.c) The salt-solvent, salt-diluent, and diluent-solvent solubilities jointly determine the solvation structures in LHCE. For example, at certain concentrations, the Li+ solvation shells contain both anions and solvent molecules with minimal participation of the diluent molecules. The local salt concentration can be even higher than its counterpart in the HCE. These simulated solvation structures in bulk electrolytes compare well with Raman spectrum and SAXS data.d) Moreover, the solvation structures are temperature-sensitive. We revealed why the local salt concentration is higher at a certain temperature by MD simulations, which is further validated through Raman deconvolution analyses.e) The SEI formation is sensitive to the electrolyte structure near a charged surface. Therefore, the electrical double-layer (EDL) structure of LHCE needs to be resolved. Here we give a statistical representation of the LHCE in the EDL and show how it differs from the bulk structure and its impact on SEI formation.Reference:[1] J. Electrochem. Soc., 2021, 168, 010522[2] Nat. Energy 2019, 4, 796-805

(Invited) Modeling the Charge Transfer Reactions at Li/SEI/Electrolyte Interfaces in Lithium-Ion Batteries

Two kinds of charge transfer reactions are critical for the performance and life of lithium battery: the desired ion transfer reaction occurring during each charge/discharge cycle, , and the undesired electron transfer reactions leading to the parasitic chemical decomposition of the electrolyte and solid electrolyte interphase (SEI) formation/growth. The heterogeneous multi-component nature of SEI dominates its ionic and electronic transport properties and controls these two charge transfer reactions. Density Functional Theory (DFT)-informed multiscale modeling has been providing valuable insights under the scarcity of quantitative experiments. For example, the LiF/Li2CO3 interface was demonstrated to increase the ionic conductivity of mixed SEI nanocomposite by forming an ionic space charge region near the interface and promoting more Li-ion interstitials in Li2CO3, although LiF itself has low Li-ion conducting carriers and conductivity. To form a LiF-rich SEI layer, the electrolyte compositions need to be designed. Since the SEI formation occurs on the charged surface, the electric double layer (EDL) structure near the charged surfaces needs to be incorporated into the modeling. Here interactive classical molecular dynamics (MD), DFT, and data statistical analysis were combined 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. It was found the effectiveness of adding fluoroethylene carbonate (FEC) to form the beneficial F-containing SEI component (e.g., LiF) varies with the electrolyte and temperature, because of the interplay of ion-solvent interactions with the surface charge. These integrated modeling provided quantitative guidance for electrolyte/SEI/Li-metal interface design.

Reveal the Electrical Double Layer (EDL) in Zinc Battery Electrolytes with Electrocapillarity

The electrified interface between electrodes and electrolytes, aka, electrical double layer (EDL), resides at the heart of electrochemistry and exists universally in all electrochemical devices. It governs the kinetics and reversibility of all electrochemical processes, and predicts the interphase chemistries in advanced batteries. However, despite such importance, its understanding remains insufficient. While many theoretical models have been developed to predict EDL structure and to correlate key properties to the structures, so far there have been very rare direct experimental characterization, due to the limitations of existing techniques and the extreme elusiveness and sensitivity of the electrified interfaces.In this talk, I will discuss a modernized high-resolution electrocapillarity method, developed in my group. Applying this reborn electrocapillarity on a bivalent electrolyte of ZnCl2 and ZnSO4, we reveal the interfacial structure of Zn ion battery electrolytes in the absence and presence of anion specific adsorption and established the abnormal potential distribution across the interface due to anion adsorption and its effect on the kinetics of Zn ion deposition chemistry.

Structure and Dynamics of the Electrical Double Layer during the Rapid Alternating Polarity Electro-Synthesis

Conventional electrochemical organic synthesis uses direct current (DC) condition, where the electrode polarity is not changed during the operation. Unlike DC, alternating current (AC) introduces two more tunable parameters into the potential or current profile: frequency and waveform, allowing new possibilities for modulating reaction efficiency and selectivity. Several very recent AC electrosynthesis examples have shown that the AC can lead to enhanced chemoselectivity that cannot be reproduced by their DC counterparts1–3. For instance, Hayashi et al. presented a highly selective and easily scalable Birch-type reduction of heteroarenes by rapid alternating polarity (rAP) waveform3. AC voltage transforms the reaction kinetics presumably by affecting the mass transfer of reactive species both in the bulk solution and the electrical double layers (EDL). However, the mechanistic origin of the unique reactivity in AC electrosynthesis is underexplored. Molecular-level details are still in lack to possibly guide the rational design of AC reaction parameters.In this study, we have chosen the rAP heteroarene reduction as the example system and employed classical molecular dynamics (MD) simulations to reveal the liquid structure and dynamics in bulk and interfacial electrolyte. To capture the electrode-electrolyte interfaces, a slab-geometry simulation cell was used, where a 10 nm thick liquid electrolyte is sandwiched between two oppositely charged graphene surfaces. The multicomponent electrolyte was composed of ethanol and tetrahydrofuran (THF) as the co-solvent, [(CH3)4N]+[(BF4)]- as the salt, and a heteroarene substrate. Based on the charge distribution function statistics, the EDL layer was about 1 nm thick, so if any of the oxygen atom in the ethanol or THF is within 6 Å to the electrode surface, they are considered to be within the EDL. Under both AC and DC, the ethanol to THF ratio was higher than that in the bulk electrolyte due to stronger ion-ethanol attraction. The EDL structure responded to electric field polarity change at different time scales. First, the molecule orientation would flip also within the picosecond time scale after the polarity switch. By tracking the number of molecules in the EDL, we have found that the compositional fluctuation in the EDL converges in about 40 ps. Although it is the ion migration that gets directly affected by the alternating electric field, diffusion of charge-neutral molecules was also found to be accelerated under AC, according to the higher mean squared displacement calculated from the movement of all molecules of each species in the simulation box. This accelerated diffusion spans a larger length and longer time scales. A multi-scale model is proposed to describe both reaction kinetics and liquid structure dynamics simultaneously.

Novel carbon-based composites enriched with Fe and Mn as effective and eco-friendly adsorbents of heavy metals in multicomponent solutions

With increasing demand for adsorbents highly effective in pollutant removal, carbon-based porous materials are becoming more and more popular. In this work, a new approach to the synthesis of such solids using an environmentally friendly, two-step preparation method is presented. A series of hybrid porous silica-containing carbon composites was synthesized, namely: metal free (C/SiO2), enriched with manganese (C/Mn/SiO2), as well as iron (C/Fe/SiO2). The effect of additives on the structure and morphology of the composites was evaluated using X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption and scanning electron microscope (SEM). The as-synthesized carbons were used as effective adsorbents for the simultaneous removal of heavy metals, including lead (Pb(II)) and zinc (Zn(II)) ions. In particular, it was determined that C/Mn/SiO2 sample demonstrated the highest adsorption capacity towards Pb(II) and Zn(II) ions. It was equal to 211.60 mg/g for Pb(II) and 74.95 mg/g for Zn(II). Zeta potential and surface charge density of the solids, with and without metals, were investigated to determine electrical double layer structure, whereas stability studies and aggregate size measurements were performed to estimate solid aggregation under selected conditions. It was established that solids with adsorbed metals formed suspensions with lower stability than those without ions. This, in turn, facilitates their separation from aqueous solutions.

Tuneable interphase transitions in ionic liquid/carrier systems via voltage control

The structure and interaction of ionic liquids (ILs) influence their interfacial composition, and their arrangement (i.e., electric double-layer (EDL) structure), can be controlled by an electric field. Here, we employed a quartz crystal microbalance (QCM) to study the electrical response of two non-halogenated phosphonium orthoborate ILs, dissolved in a polar solvent at the interface. The response is influenced by the applied voltage, the structure of the ions, and the solvent polarizability. One IL showed anomalous electro-responsivity, suggesting a self-assembly bilayer structure of the IL cation at the gold interface, which transitions to a typical EDL structure at higher positive potential. Neutron reflectivity (NR) confirmed this interfacial structuring and compositional changes at the electrified gold surface. A cation-dominated self-assembly structure is observed for negative and neutral voltages, which abruptly transitions to an anion-rich interfacial layer at positive voltages. An interphase transition explains the electro-responsive behaviour of self-assembling IL/carrier systems, pertinent for ILs in advanced tribological and electrochemical contexts.

Desalination performance of shale gas produced water by flow-electrode capacitive deionisation process

The cost-effective desalination of shale-gas produced water (PW) has long been an industrial research hotspot. Flow-electrode capacitive deionisation (FCDI), a recently developed electrochemical desalination technology, may be a novel option for PW disposal because of its attractive advantages. However, reports on the desalination test of actual high-salinity industrial wastewater by FCDI are lacking. In this study, a laboratory-scale FCDI device with an online monitoring system was used to desalinate shale-gas PW. FCDI achieved relatively stable desalination efficiency for pretreated PW with a salinity of 2.65 % and reached an energy-normalised salt removal of 0.479 mg/J. The flow electrode chemically activated by KOH increased the FCDI average desalination rate by 98.5 % for the pretreated saline PW. Electrochemical impedance spectroscopy analysis revealed that the majority of fouling accumulated on the anion-exchange membrane (AEM) side. Residual pollutants were adsorbed by the flow electrode in the AEM chamber, which destroyed the optimal ion-transport path and electric double-layer structure. Results showed that FCDI was more suitable for PW’s reverse-osmosis (RO) permeate desalination to form an RO–FCDI hybrid. This study provided a practical experimental case on the electrochemical desalination of saline PW by FCDI.

Microscopic Origin of Electrochemical Capacitance in Metal-Organic Frameworks.

Electroconductive metal-organic frameworks (MOFs) have emerged as high-performance electrode materials for supercapacitors, but the fundamental understanding of the underlying chemical processes is limited. Here, the electrochemical interface of Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with an organic electrolyte is investigated using a multiscale quantum-mechanics/molecular-mechanics (QM/MM) procedure and experimental electrochemical measurements. Our simulations reproduce the observed capacitance values and reveals the polarization phenomena of the nanoporous framework. We find that excess charges mainly form on the organic ligand, and cation-dominated charging mechanisms give rise to greater capacitance. The spatially confined electric double-layer structure is further manipulated by changing the ligand from HHTP to HITP (HITP = 2,3,6,7,10,11-hexaiminotriphenylene). This minimal change to the electrode framework not only increases the capacitance but also increases the self-diffusion coefficients of in-pore electrolytes. The performance of MOF-based supercapacitors can be systematically controlled by modifying the ligating group.

Specific adsorption induced electric double layer on gallium-based liquid metal electrode

Gallium-based liquid metal (GBLM) has been identified as a promising electrode material in flexible aqueous batteries, which are widely employed in wearable electronic devices. The electrode–electrolyte interface has significant effects on battery performance, but its molecular-level structure remains elusive. This work, for the first time, attempts to unravel electric double layer (EDL) at the interface between GBLM electrode and aqueous electrolyte through density functional theory (DFT) calculation and ab initio molecular dynamic (AIMD) simulation. It is found that such EDL structure origins from the specific adsorption of gallates (e.g. Ga(OH)4− and H2GaO3−) on GBLM (e.g. eutectic gallium-indium alloy), and these gallates build up the inner Helmholtz layer (IHL), attracting a diffusion layer with opposite charges. Further, the adsorption properties of gallates and the capacitive behavior of EDL are analyzed, in which the charging of GBLM electrode is systematically considered. The results manifest that the excess negative charge on GBLM surface interferes with the adsorbed gallates and amplifies the interface potential change across EDL. The proposed EDL structure contributes to deep understandings of the electrochemical processes occurring at electrode–electrolyte interface in GBLM aqueous batteries.

Ag/Reduced Graphene Oxide/Carbon Fiber Composites as Electrodes for Highly Stable and Responsive Marine Electric Field Sensors

The increasing demand for maintenance-free, cost-effective, and high-stability flexible electrodes is highly anticipated for the research of marine electric-field sensors, and various carbon fibers (CFs) are considered the most suitable carbon-based electrode for the purpose. Nevertheless, the conventional fabrication of acidified or nitrogenized CF electrodes did not attract great attention for commercial application, which has limitations in the case of simultaneous cost-effectiveness and long-term stability. In this study, with homemade reduced graphene oxide (rGO) load, the prepared double carbon substrate Ag-rGO-CF composite electrodes have a honeycomb rGO conductive skeleton and the dispersed Ag nanoparticles via a facile hermetic oxidation process and hydrothermal method. The prepared Ag-rGO-CF composite electrode demonstrated an outstanding electrode performance, including low resistance, high electrochemical reaction rate, and stable potential with long-term stability and low cost. The electric double-layer (EDL) structure theory from the Gouy–Chapman–Stern model and double carbon substrate mechanism between CFs and rGO with the help of Ag were clarified, whose principle is to strengthen the adsorption force and electrostatic attraction of the electrode and to offset the residual charge while reducing the thickness of the electric double layer to achieve the purpose of potential balance. The Ag-rGO-CF composite electrode has presented long-term stability and high sensitivity, especially a wide application bandwidth. The Ag-rGO-CF composite electrode made in this study is a competitive candidate material as a flexible marine electrode field sensor.

Electric double layer contribution to sum frequency generation signal from Au electrode.

Understanding the electric double layer (EDL) of the metal electrode-electrolyte interface is essential to electrochemistry and relevant disciplines. In this study, potential-dependent electrode Sum Frequency Generation (SFG) intensities of polycrystalline gold electrodes in HClO4 and H2SO4 electrolytes were thoroughly analyzed. The potential of zero charges (PZC) of the electrodes was -0.06 and 0.38V in HClO4 and H2SO4, respectively, determined from differential capacity curves. Without specific adsorption, the total SFG intensity was dominated by the contribution from the Au surface and increased similar to that of the visible (VIS) wavelength scanning, which pushed the SFG process closer to the double resonant condition in HClO4. However, the EDL contributed about 30% SFG signal with specific adsorption in H2SO4. Below PZC, the total SFG intensity was dominated by the Au surface contribution and increased with potential at a similar slope in these two electrolytes. Around PZC, as the EDL structure became less ordered and the electric field changed direction, there would be no EDL SFG contribution. Above PZC, the total SFG intensity increased much more rapidly with potential in H2SO4 than in HClO4, which suggested that the EDL SFG contribution kept increasing with more specific adsorbed surface ions from H2SO4.