Electrode / electrolyte interface double layer formation

The properties characteristic for electrochemical nonlinear phenomena are determined by the electrical properties of electrochemical systems, most importantly the potential drop across the electrochemical double layer at the working electrode (WE). Compared to the characteristic length scales of the patterns that develop, the extension of the double layer perpendicular to the electrode can be ignored.2 The potential drop across the double layer can therefore be lumped into one variable, DL, and the temporal evolution law of DL at every position r along the (in general two-dimensional) electrode electrolyte interface is the central equation of any electrochemical model describing pattern formation.3 It results from a local charge bal-... 

These deviations are caused by electrode polarization owing to double layer formation in electrode-electrolyte interface. Only the semicircle refleets the bulk conductivity of the polymer electrolyte. In contrast to PEO, ENR-25 displays even at high salt contents dramatic electrode polarization effects. This dominating electrode polarization disappears only at high salt concentrations, Y > 0.2. 

Note that in practice, experimental spectra — especially at low frequencies — may also contain contributions originating from the electrode/electrolyte interface. A typical example is electrode polarizaticHi arising from the formation of a diffuse double layer of ions close to a charged surface. Partly, such features depend on the dielectric properties of the electrolyte solution (our focus), but in essence, they are specific to the interface and thus are not topic of this contribution. However, such electrode processes are intensively studied in electrochemistry using, e.g., impedance spectroscopy. 

At the anode electrode-electrolyte interface, there is an increase in the electrical potential owing to the formation and accumulation of charge species in the electrical double layer that spans over the anode-electrolyte interface. 

While the formation of an electrical double layer at interfaces is a general phenomenon, the electrode-electrolyte solution interface will be considered... 

In its most simple form, this means without effects such as adsorption or formation of coatings at the electrode surface36. The resistance, Rc, represents electrical conductivity of the electrolyte and is not a property of the electrode itself. The differential double-layer capacity, Cmetal surface of the metal-electrolyte interface, which is in equilibrium with an equal excess of charge but opposite in sign at the side of the electrolyte. 

The formation of 2D Meads phases on a foreign substrate, S, in the underpotential range can be well described considering the substrate-electrolyte interface as an ideally polarizable electrode as shown in Section 8.2. In this case, only sorption processes of electrolyte constituents, but no Faradaic redox reactions or Me-S alloy formation processes are allowed to occur, The electrochemical double layer at the interface can be thermodynamically considered as a separate interphase [3.54, 3.212, 3.213]. This interphase comprises regions of the substrate and of the electrolyte with gradients of intensive system parameters such as chemical potentials of ions and electrons, electric potentials, etc., and contains all adsorbates and all surface energy. Furthermore, it is assumed that the chemical potential //Meads is a definite function of the Meads surface concentration, F, and the electrode potential, E, at constant temperature and pressure Meads (7", ). Such a model system can only be... 

Thus, in the metal/YSZ systems of solid-state electrochemistry, AC-impedance spectroscopy provides concrete evidence for the formation of an effective electrochemical double layer over the entire gas-exposed electrode surface. The capacitance of this metal/gas double layer is of the order of 100-500 pF cm-2 of superficial electrode surface area and of the order 2-10 pF cm-2 when the electrode roughness is taken into account and, thus, the true metal/gas interface surface area is used, comparable to that corresponding to the metal/solid electrolyte double layer. Furthermore AC-impedance spectroscopy... 

When a metal electrode is placed in an electrolyte solution, an equilibrium difference usually becomes established between the metal and solution. Equilibrium is reached when the electrons left in the metal contribute to the formation of a layer of ions whose charge is equal and opposite to that of the cations in solution at the interface. The positive charges of cations in the solution and the negative charges of electrons in the metal electrode form the electrical double layer [4]. The solution side of the double layer is made up of several layers as shown in Fig. 2.7. The inner layer, which is closest to the electrode, consists of solvent and other ions, which are called specifically adsorbed ions. This inner layer is called the compact Helmholtz layer, and the locus of the electrical centers of this inner layer is called the inner Helmholtz plane, which is at a distance of di from the metal electrode surface. The solvated ion can approach the electrode only to a distance d2. The locus of the centers of the nearest solvated ion is called the outer Helmholtz plane. The interaction of the solvated ion with metal electrode only involves electrostatic force and is independent of the chemical properties of the ions. These ions are called non-specifically adsorbed ions. These ions are distributed in the 3D region called diffusion layer whose thickness depends on the ionic concentration in the electrolyte. The structure of the double layer affects the rate of electrode reactions. 

Electrochemical microsystem technology can be scaled down from macroscopic science to micro and further to nanoscale through EMST to ENT [1]. In ENT, electrochemistry involves in the production process to realize nanoproducts and systems which must have reproducible capability. The size of the products and systems must be in the submicron range. It considers electrochemical process for nanostructures formation by deposition, dissolution and modification. Electrochemical reactions combining ion transfer reactions (ITR) and electron transfer reactions (ETR) as applicable in EMST are also applied in ENT. Molecular motions play an important role in ENT as compared with EMST. Hence, mechanical driven system has to be changed to piezo-driven system to achieve nanoscale motions in ENT. Due to the molecular dimension of ENT, quantum effects are always present which is not important in the case of EMST. The double layer acts as an interface phenomenon between electrode and electrolyte in EMST, however, double layer in the order of few nanometers even in dilute electrolyte interferes with the nanostmcture in ENT. 

Nanocell is the smallest electrochemical cell developed by Sugimura and Nakagiri [11] and further developed and utilized for ENT by BloeB et al. [10]. The nanocell consists of two electrodes distance between electrodes is generally maintained in the order of less than 1 nm. In between two electrodes, absorbed water film acts as an electrolyte whose volume is maintained by vapor pressure and ranges from 10 to 10 cm. Double layer capacitance is not formed across the solid liquid interface in the nanocell due to the much smaller inter-electrode gap and hence, generated hydrogen ion and hydroxyl ion recombine immediately. Nanotip of microtool such as tip of scanning probe microscope (SPM) or AFM tip is most suitable for the formation of electrochemical nanoceU. 

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