Properties Of Electrical Double Layer Research Articles

Modeling heat transfer of nanofluid flow in microchannels with electrokinetic and slippery effects using Buongiorno’s model

PurposeThis paper aims to study the heat transfer of nanofluid flow driven by the move of channel walls in a microchannel under the effects of the electrical double layer and slippery properties of channel walls. The distributions of velocity, temperature and nanoparticle volumetric concentration are analyzed under different slip-length. Also, the variation rates of flow velocity, temperature, concentration of nanoparticle, the pressure constant, the local volumetric entropy generation rate and the total cross-sectional entropy generation are analyzed.Design/methodology/approachA recently developed model is chosen which is robust and reasonable from the point of view of physics, as it does not impose nonphysical boundary conditions, for instance, the zero electrical potential in the middle plane of the channel or the artificial pressure constant. The governing equations of flow motion, energy, electrical double layer and stream potential are derived with slip boundary condition presented. The model is non-dimensionalized and solved by using the homotopy analysis method.FindingsSlip-length has significant influences on the velocity, temperature and nanoparticle volumetric concentration of the nanofluid. It also has strong effects on the pressure constant. With the increase of the slip-length, the pressure constant of the nanofluid in the horizontal microchannel decreases. Both the local volumetric entropy generation rate and total cross-sectional entropy generation rate are significantly affected by both the slip-length of the lower wall and the thermal diffusion. The local volumetric entropy generation rate at the upper wall is always higher than that around the lower wall. Also, the larger the slip-length is, the lower the total cross-sectional entropy generation rate is when the thermal diffusion is moderate.Originality/valueThe findings in this work on the heat transfer and flow phenomena of the nanofluid in microchannel are expected to make a contribution to guide the design of micro-electro-mechanical systems.

Nanoscale Fluid Vortices and Nonlinear Electroosmotic Flow Drive Ion Current Rectification in the Presence of Concentration Gradients.

Ion current rectification (ICR) is a transport phenomenon in which an electrolyte conducts unequal currents at equal and opposite voltages. Here, we show that nanoscale fluid vortices and nonlinear electroosmotic flow (EOF) drive ICR in the presence of concentration gradients. The same EOF can yield negative differential resistance (NDR), in which current decreases with increasing voltage. A finite element model quantitatively reproduces experimental ICR and NDR recorded across glass nanopipettes under concentration gradients. The model demonstrates that spatial variations of electrical double layer properties induce the nanoscale vortices and nonlinear EOF. Experiments are performed in conditions directly related to scanning probe imaging and show that quantitative understanding of nanoscale transport under concentration gradients requires accounting for EOF. This characterization of nanopipette transport physics will benefit diverse experimentation, pushing the resolution limits of chemical and biophysical recordings.

Induced polarization of volcanic rocks. 3. Imaging clay cap properties in geothermal fields

Smectite-rich clay caps form permeability seals in geothermal systems. The presence of smec-tite is also responsible for a strong surface (interfacial) electrical conductivity and polarization due to their electrical double layer properties. We developed new complex conductivity models using both differential effective medium (DEM) and volume averaging theories accounting for both conduction and polarization of these high cation exchange capacity (CEC) materials. These models predict that the chargeability is also a non-linear function of the pore water conductivity reaching a constant value at pore water conductivity far above the so-called iso-conductivity point. The iso-conductivity point is characterized by the equality between the conductivity of the rock and the conductivity of the pore water. We apply the DEM conductivity model (which requires only two textural parameters) to smectite-rich volcanic and sedimentary rocks using data sets from the literature. When smectite is present in the volcanic rocks, the CEC of the rock is dominated by the CEC of smectite. The grain conductivity and the normalized chargeability are related to each other by a dimensionless number R = 0.10 (independent of temperature and saturation) and both are controlled by the excess of charge per unit pore volume Q V , which can be determined from the CEC and porosity. Our petro-physical model is also able to predict the permeability of the rock as well from the CEC and the porosity. It is applied to a 3-D data set at Krafla volcano (Iceland). The porosity, the CEC, the percentage of smectite, and the permeability of the clay-cap are imaged by 3-D induced polarization tomography. Electrical conductivity tomography alone does not allow separation of the contribution of the bulk pore space from the interfacial properties related to alteration and therefore should be used with caution.

Solution Structure Effects on the Properties of Electric Double Layers with Surface Charge Regulation Assessed by Density Functional Theory.

The structure of electrolyte solutions in electric double layers is primarily determined by the solvent, despite the fact that it is usually neutral and not subject to Coulombic interactions. The number of solvent molecules in a typical electrolyte solution may be significantly greater that the number of ions. Hence, the charged species compete for space with a much larger number of neutral molecules, which has a strong effect on the density distributions near charged surfaces. Even for very dilute electrolyte solutions, the density profiles resemble liquidlike structure, which is entirely due to the presence of the dense solvent. Our work demonstrates that the solvent structural effect strongly couples to the surface chemistry, which governs the charge and potential. We argue that a comprehensive statistical-mechanical approach, such as classical density functional theory that explicitly includes all solution species, in combination with a surface charge regulation condition at the interface, provides an excellent approach for describing charged interfaces. It allows for revealing important physical features and includes non-Coulombic contributions such as ionic and surface solvation.

Dielectric relaxation spectroscopy of aqueous micellar electrolyte solutions: A novel application to infer Dukhin number and zeta potential of a micelle.

The complex permittivities of aqueous SDS solutions, with and without the addition of sodium chloride (NaCl), are measured in the frequency range from 200 MHz to 14 GHz. The SDS concentrations are chosen such that the SDS molecules aggregate to micelles. In this frequency range, the measured spectra allow for the identification of two different relaxation processes. That is, the relaxation of the water molecules at frequencies above 1 GHz and the micellar relaxation at frequencies lower than 1 GHz. It is found that the addition of NaCl to the system mostly affects the micellar relaxation process. In detail, the time constant as well as the amplitude of the relaxation decrease by adding NaCl. These effects are attributed to the change in the solution conductivity that changes the properties of the micelle's electrical double layer. We also extract the Dukhin number of the micelles as a function of surfactant and electrolyte content from the measurements. The Dukhin number is a dimensionless group that describes the influence of the surface conductivity on a phenomena. A regression between Dukhin numbers and free sodium ions is found so that all data collapses on a single curve independent of the surfactant concentration. The surface conductivity is a manifestation of the electrical double layer and we use the Bikerman equation to infer the zeta potential of the micelles. Comparison to literature data shows very good agreement and proves that dielectric relaxation spectroscopy can be engaged to infer the zeta potential of micelles. Abbreviations: CMC critical micelle concentration, DRS dielectric relaxation spectroscopy, EDL electrical double layer.

What is the effect of polar and nonpolar side chain group on bulk and electrical double layer properties of amino acid ionic liquids?

Two amino acid ionic liquids (AAILs) were investigated by molecular dynamics simulation to get effect of polar group at bulk of liquid and adsorb layer of electric double layer. Hydrogen bond plays an important role in this evaluation. Polar group changed hydrogen bond site of the pure bulk. By introducing AAILs on the graphene surface, the total number of hydrogen bonds was increased and hydrogen bond site was changed in the case of common ionic liquid. It was also observed anion-anion self-hydrogen bond is probable for AAILs. Graphene surface decreases the number of this self-hydrogen bonds. Potential of mean force was also obtained to find adsorption or desorption free energy of AAILs near the surface. The interaction of anion with the surface is weakened if anion of AAIL contains polar group. Responsing with lower potential is an important factor in using an IL as an electrolyte in supercapacitors. Polar group decreases the response potential of the AAIL.

Structural analysis of an amino acid ionic liquid: Bulk and electrical double layer

The interfacial structures and macroscopic properties of electrical double layer for 1-ethyl-3-methyl-imidazolium phenyl alanine ([EMIM][PHE]), as an amino acid ionic liquid (AAIL), have been investigated by molecular dynamics simulation and compared with conventional [EMIM][PF6] IL. Results of bulk state showed that hydrogen atoms of ring in [EMIM]+ are capable to form hydrogen bond with the nitrogen and oxygen of [PHE]−. The number of these hydrogen bonds enhances if IL is introduced to graphene sheet. Surprisingly, it was observed that anion-anion hydrogen bond is also probable for [EMIM][PHE]. Introducing the AAIL to graphene does not affect number of this anion-anion hydrogen bond. Being in touch with graphene or not, the main correlation regime between anion and cation is the tail-ring for studied systems. It was observed that phenyl ring of [PHE]− acts as an inhibitor for [EMIM]+ to form π-π stacking with graphene. This behavior leads to higher accumulation of [PHE]− than [EMIM]+ in the first layer. In the current study, a responding electrical potential for an assumed supercapacitor was also introduced. Responding potential of [EMIM][PHE] is lower than [EMIM][PF6].

Solvophilic and solvophobic surfaces and non-Coulombic surface interactions in charge regulating electric double layers.

The properties of electric double layers are governed by the interface between the substrate and the adjacent electrolyte solution. This interface is involved in chemical, Coulombic, and non-Coulombic (e.g., van der Waals or Lennard-Jones) interactions with all components of the fluid phase. We present a detailed study of these interactions using a classical density functional approach. A particular focus is placed on the non-Coulombic interactions and their effect on the surface chemistry and charge regulation. The solution structure near the charged interface is also analyzed and used to offer a thorough interpretation of established concepts such as the Stern and diffuse ionic layers.

Insight into the dielectric response of transformer oil-based nanofluids

The oil-based nanofluids with greater dielectric strength have attracted much attention as a crucial insulating materials in high-voltage oil-immersed power equipment. In fact, the different microstructures of the transformer oil-based nanofluids (TNFs) would result in different dielectric properties. In this work, the broadband dielectric spectroscopy measurement was used to establish the linkage between the electric double layer (EDL) and dielectric response properties of TNFs which was performed at 298K temperature and with frequency range from 10-2Hz∼106Hz. The modified Havriliak-Negami (HN) model function was used to analyze the measured results. The results demonstrate that both the real and imaginary parts of dielectric spectra of two kinds of oil are composed of the conductivity and polarization process. Compared with pure oil, two polarization process could be observed for the TNFs, explained by the EDL structure reasonably. The introduction of the EDL structure provides an idea to account for the insulating strength improvement of TNFs for the first time.

Influence of Indifferent Electrolytes on Formation of Coagulative Structures in Aqueous Silica Dispersions

Effects of indifferent electrolytes (NaCl, KCl, LiCl, NaI, NaNO3, CaCl2, and MgCl2) on the electrical double layer (EDL), aggregation, gelling, and rheological properties of aqueous dispersions of nanosilica were investigated. All examined indifferent electrolytes enhance interactions between nanoparticles of fumed silica through the coagulation mechanism. The critical concentration of gelation and gelling time decrease in the presence of the electrolytes, while the effective viscosity of the dispersions and average size of aggregates (Def) increase in series of chlorides: Li+ < Na+ < K+ < Ca2+ < Mg2+. That corresponds to an increase in the cation radius and reduction of the hydration shell. The nature of anions and cations significantly affects the values of Def and viscosity. For sodium salts, the viscosity increases in series I- < NO3- < Cl- corresponding to an increase in the hydration shell.

Electrical double layer properties of spherical oxide nanoparticles.

The accurate characterization of the electrical double layer properties of nanoparticles is of fundamental importance for optimizing their physicochemical properties for specific biotechnological and biomedical applications. In this article, we use classical solvation density functional theory and a surface complexation model to investigate the effects of the pH and the nanoparticle size on the structural and electrostatic properties of an electrolyte solution surrounding a spherical silica oxide nanoparticle. The formulation has been particularly useful for identifying dominant interactions governing the ionic driving force at a variety of pH levels and nanoparticle sizes. As a result of the energetic interplay displayed between electrostatic potential, ion-ion correlation and particle crowding effects on the nanoparticle surface titration, rich, non-trivial ion density profiles and mean electrostatic potential behavior have been found.

Dielectric and magnetic characterizations of capacitor structures with an ionic liquid/MgO barrier and a ferromagnetic Pt electrode

The dielectric and magnetic properties of electric double layer (EDL) capacitor structures with a perpendicularly magnetized Pt/Co/Pt electrode and an insulating cap layer (MgO) are investigated. An electric field is applied through a mixed ionic liquid/MgO barrier to the surface of the top Pt layer, at which the magnetic moment is induced by the ferromagnetic proximity effect. The basic dielectric properties of the EDL capacitor are studied by varying the thickness of the MgO cap layer. The results indicate that the capacitance, i.e., the accumulated charge density at the Pt surface, is reduced with increasing the MgO thickness. From the MgO thickness dependence of the capacitance value, the effective dielectric constant of the ionic liquid is evaluated. Almost no electric field effect on the magnetic moment, the coercivity, or the Curie temperature is confirmed in the top Pt layer with the thickness of 1.3 nm, regardless of the presence or absence of the MgO cap layer, whereas the a clear change in the magnetic moment is observed when the top Pt layer is replaced by a Pd layer of 1.7 nm.

Electrolyte solution structure and its effect on the properties of electric double layers with surface charge regulation

The physical origin of charged interfaces involving electrolyte solutions is in the thermodynamic equilibrium between the surface reactive groups and certain dissolved ionic species in the bulk. This equilibrium is very strongly dependent on the precise local density of these species, also known as potential determining ions in the solution. The latter, however, is determined by the overall solution structure, which is dominated by the large number of solvent molecules relative to all solutes. Hence, the solvent contribution to the molecular structure is a crucial factor that determines the properties of electric double layers. Models that explicitly account for the solvent structure are often referred to as “civilized” as opposed to the “primitive” ones that consider the solvent as a structureless continuum. In the present paper, we demonstrate that for a physically correct description of charged interfaces that involve electrolyte solutions (electric double layers), the full solution structure needs to be taken into account in conjunction with the precise surface chemistry governed by the thermodynamic equilibrium. The analysis shows how the surface charge depends on various experimentally relevant parameters, many of which are outside the realm of simple electrostatics. We present results on the effects of solvent molecular dimensions, ionic solvation, surface chemistry, solvophilicity and solvophobicity.

Boosting the Performance of Ionic-Liquid-Based Supercapacitors with Polar Additives

Recent years have witnessed growing interests in both the fundamentals and applications of electric double layer capacitors (EDLCs), also known as supercapacitors. A number of strategies have been explored to optimize the device performance in terms of both the energy and power densities. Because the properties of electric double layers (EDL) are sensitive to ion distributions in the close vicinity of the electrode surfaces, the supercapacitor performance is sensitive to both the electrode pore structure and the electrolyte composition. In this work, we study the effects of polar additives on EDLC capacitance using the classical density functional theory within the framework of a coarse-grained model for the microscopic structure of the porous electrodes and room-temperature ionic liquids. The theoretical results indicate that a highly polar, low-molecular-weight additive is able to drastically increase the EDLC capacitance at low bulk concentration. Additionally, the additive is able to dampen the oscill...

Effect of aqueous‐based cathode slurry pH and immersion time on corrosion of aluminum current collector in lithium‐ion batteries

Corrosion of aluminum can occur during the manufacturing of lithium‐ion batteries when using aqueous‐based cathode slurries. In exposure tests, the alkaline pH value of aqueous‐based cathode slurries and immersing time were revealed as the principle factors that control the corrosion of aluminum during the cathode manufacturing process. The nickel manganese cobalt oxide active material used in the slurry does not have a direct impact on corrosion of the aluminum current collector. The initiation and evolution of localized corrosion on aluminum are closely related to the formation of galvanic cells between aluminum matrix and intermetallic particles. X‐ray photoelectron spectroscopy results confirmed that the pH of cathode slurry was the only factor that alters aluminum surface composition, during which the oxide passive film was gradually degraded into hydroxide. Electrochemical characterizations showed that aluminum electrodes gave remarkably different response to the different pH of test solutions. The time‐pH‐variant electrochemical response was ascribed to the change of passive film and electric double layer properties.

Hierarchical micro & mesoporous silicon carbide flakes for high-performance electrochemical capacitive energy storage

Hierarchical micro/mesoporous silicon carbide flakes (SiCF) with a high surface area of about 1376 m2 g−1 are obtained by one-step carbonization of waste Si wafer without any chemical or physical activation. The micropores are derived from the partial evaporation of Si atoms during the carbonization process and mesopores are formed by the integration of neighboring micropores. During carbonization process, the proportion of micro and mesopores in SiCF can be controlled by carbonization time by controlling the amount of partial evaporation of Si atoms. The SiCF electrode carbonized for 8 h at 1250 °C exhibits high charge storage capacity with a specific capacitance of 203.7 F g−1 at a scan rate of 5 mV s−1 with 87.3% rate performance from 5 to 500 mV s−1 in 1 M KCl aqueous electrolyte. The outstanding electrochemical performance can be the synergistic effect of both enhanced electric double layer properties caused by micropores and reduced resistant pathways for ions diffusion in the pores as well as a large accessible surface area for ion transport/charge storage caused by mesopores. These encouraging results demonstrate that the SiCF carbonized for 8 h at 1250 °C can be promising candidate for high performance electrode materials for supercapacitors.

Oxygen-doped porous silicon carbide spheres as electrode materials for supercapacitors.

Oxygen-containing functional groups were introduced onto the surface of the micro- and meso-porous silicon carbide sphere (MMPSiC) in order to investigate the relationship between the electric double layer properties and pseudo-capacitive properties; the degree of oxidation of MMPSiC was also optimized. Although the oxygenated surface functionalities can lead to a decrease in the surface area of MMPSiC, the oxygen functional groups attached to the external surface can participate in the redox reaction, resulting in the enhancement of the total super-capacitive performance. The MMPSiC electrode oxidized for 24 h exhibits a high charge storage capacity with a specific capacitance of 301.1 F g(-1) at a scan rate of 5 mV s(-1), with 86.8% rate performance from 5 to 500 mV s(-1) in 1 M KCl aqueous electrolyte. This outstanding capacitive performance of the MMPSiC electrode oxidized for 24 h can be attributed to the harmonious synergistic effect between the electric double layer capacitive contribution of MMPSiC and the pseudo-capacitive contribution of the oxygen-containing functional groups. These encouraging results demonstrate that the MMPSiC electrode oxidized for 24 h is a promising candidate for high performance electrode materials for supercapacitors.

Carbonization temperature dependence of pore structure of silicon carbide spheres and their electrochemical capacitive properties as supercapacitors

Three-dimensional silicon carbide-based frameworks with hierarchical micro- and mesoporous structures (2MSiC) are prepared by employing the template method and carbonization reaction using aerosol-spray drying. The mesopores are generated by the self-assembly of a structure-directing agent, whereas the micropores originate from the partial evaporation of Si atoms during the carbonization process. During the carbonization process, the proportion of micro- and mesopores in 2MSiC can be controlled by the carbonization temperature by controlling the amount of partial evaporation of Si atoms. The 2MSiC electrode prepared using a Brij56 structure-directing agent as the mesopore template and carbonized at 1250°C exhibits a high charge storage capacity with a specific capacitance of 259.9Fg−1 at a scan rate of 5mVs−1 with 88.1% rate performance from 5 to 500mVs−1 in 1M KCl aqueous electrolyte. This outstanding electrochemical performance can be attributed to the synergistic effect of both the enhanced electric double layer properties caused by micropores and reduced resistant pathways for ion diffusion in the pores as well as a large accessible surface area for ion transport/charge storage caused by mesopores. These encouraging results demonstrate that the 2MSiC electrode prepared with Brij56 and carbonized at 1250°C is a promising candidate for high-performance electrode materials for supercapacitors.

A systematic comparison of different approaches of density functional theory for the study of electrical double layers.

Based on the best available knowledge of density functional theory (DFT), the reference-fluid perturbation method is here extended to yield different approaches that well account for the cross correlations between the Columbic interaction and the hard-sphere exclusion in an inhomogeneous ionic hard-sphere fluid. In order to quantitatively evaluate the advantage and disadvantage of different approaches in describing the interfacial properties of electrical double layers, this study makes a systematic comparison against Monte Carlo simulations over a wide range of conditions. The results suggest that the accuracy of the DFT approaches is well correlated to a coupling parameter that describes the coupling strength of electrical double layers by accounting for the steric effect and that can be used to classify the systems into two regimes. In the weak-coupling regime, the approaches based on the bulk-fluid perturbation method are shown to be more accurate than the counterparts based on the reference-fluid perturbation method, whereas they exhibit the opposite behavior in the strong-coupling regime. More importantly, the analysis indicates that, with a suitable choice of the reference fluid, the weighted correlation approximation (WCA) to DFT gives the best account of the coupling effect of the electrostatic-excluded volume correlations. As a result, a piecewise WCA approach can be developed that is robust enough to describe the structural and thermodynamic properties of electrical double layers over both weak- and strong-coupling regimes.

Structure of a planar electric double layer containing size-asymmetric ions: density functional approach

We have studied the structure of the electrolytes with asymmetries in charge and size near a charged planar electric double layer by a density functional theory. In the present theory, the hard-sphere contribution has been approximated as the direct pair correlation function with the coupling parameter, whereas the electronic contribution has been approximated as the mean-spherical approximation in the bulk phase. This theoretical approach for the size-symmetric and size-asymmetric electrolytes displays a good agreement with the simulation results over a wide range of surface charge densities and electrolyte concentrations. However, the accuracy between the present theory and the simulation results slightly deteriorates for the highly size-asymmetric electrolytes and the multivalent electrolytes. In these cases, the performance of the present theory is comparable to those of the simplified extension of the Poisson–Boltzmann theory and the modified Poisson–Boltzmann theory. The calculated result indicates that the surface charge distribution function, which was introduced as an indicator for studying the charge reversal, layering effect, and surface charge amplification in a planar electric double layer, describes the electronic properties of a planar electric double layer well.