Potentiostatic Current Transient Technique

The potentiostatic current transient (PCT) technique has been known as the most popular method to understand lithium transport through an intercalation electrode, based on the assumption that lithium diffusion in the electrode is the rate-determining process of lithium intercalation/deintercalation [45]. By solving Eick s second equation for planar geometry with I.C. in Equation (5.28), impermeable B.C. in Equation (5.29), and potentiostatic B.C. 

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In practical application, it was reported that the platinum particles dispersed in highly porous carbonized polyacrylonitrile (PAN) microcellular foam used as fuel-cell electrocatalyst160 have the partially active property. The fractal dimension of the platinum particles was determined to be smaller than 2.0 by using the potentiostatic current transient technique in oxygen-saturated solutions, and it was considered to be a reaction dimension, indicating that not all of the platinum particle surface sites are accessible to the incoming oxygen molecules. 

To design slurry compositions for metal CMP, usually it is necessary to determine if and how the individual additives would affect the faradaic activity of the selected metal surface. The potentiostatic current transient technique, usually combined with measurements of OCP transients, is useful for performing such tests. Figure 3.13 displays a set of experimental results to demonstrate this approach. Here the CMP metal is Cu,... 

As mentioned in potentiostatic current transient method, when the fractal dimension is determined by using diffusion-limited electrochemical technique, the diffusion layer length acts as a yardstick length.122 In the case of cyclic voltammetry, it was... 

Each of these two procedures can be varied by proceeding from a low to a high current density (or potential) or from a high to a low current density (or potential) the former is referred to as forward polarisation and the latter as reverse polarisation. Furthermore, there are a number of variations of the potentiostatic technique, and in the potentiokinetic method the pwtential of the electrode is made to vary continuously at a predetermined rate, the current being monitored on a recorder in the pulse method the electrode is given a pulse of potential and the current transient is determined by means of an oscilloscope. 

Study of the charge-transfer processes (step 3 above), free of the effects of mass transport, is possible by the use of transient techniques. In the transient techniques the interface at equilibrium is changed from an equilibrium state to a steady state characterized by a new potential difference A(/>. Analysis of the time dependence of this transition is the basis of transient electrochemical techniques. We will discuss galvanostatic and potentiostatic transient techniques for other techniques [e.g., alternating current (ac)], the reader is referred to Refs. 50 to 55. 

Potentiostatic Transient Technique, In the potentiostatic technique the potential of the test electrode is controlled, while the current, the dependent variable, is measured as a function of time. The potential difference between the test electrode and the reference electrode is controlled by a potentiostat (Fig. 6.21). The input function, a constant potential, and the response function, i = f(t), are shown in Figure 6.22. 

Two transient techniques (galvanostatic and potentiostatic) have been presented in each of these either current or potential, respectively, is kept constant during the observed variation of the other. It is hardly surprising, therefore, to discover that, since the 1950s, it has been the practice of many electrochemists to vary current and potential at the same time. The basic technique is called linear... 

An analysis of potentiostatic current density transients indicates progressive nucleation and a cluster growth controlled by hemispherical diffusion (cf. Section 6.2), as shown in Fig. 6.37. From the initial part of the transients, the nucleation rate, /, as a function of rj was determined. The number of atoms forming the critical nuclei, Afcrit -2, was determined from the slope of the log/vs. t] plot in the overpotential range - 210 mV < T <- 100 mV. These results show that localized metal deposition under electrochemical conditions using in situ local probe techniques and appropriate poiarization routines seems to be realistic. 

Potentiostatic Pulse Most applications of the potentiostatic pulse technique have involved just one surface of a metal specimen. The technique is therefore suitable for bulk specimens since only a single surface need be exposed to the electrolyte. The principle of the technique is shown schematically in Fig. 9. The metal is charged with hydrogen at a constant potential Ec for a time tc, after which the potential is stepped anodically to a value Da- The anodic step results in a current transient due to hydrogen diffusing back to the entry surface and being reoxidized. 

For the individual types of transient measuring techniques, special names exist but their terminology lacks uniformity. The potentiostatic techniques where the time-dependent current variation is determined are often called chronoamperometric, and the galvanostatic techniques where the potential variation is determined are called chronopotentiometric. For the potentiodynamic method involving linear potential scans, the term voltammetry is used, but this term is often used for other transient methods as well. 

Schrebler et al. studied the nucleation and growth mechanisms for Re deposition on polyerystalline Au electrodes, from a bath containing 0.75 mM perrhenic acid and 0.1 M sodium sulfate at pH = 2. The potentiostatic step technique was simultaneously employed with measurements of mass changes in an electrochemical quartz-crystal microbalance. The mass vs. time transients were fitted with equations deduced from the current versus time relationships of the conventional nucleation and growth models. It was concluded that electrodeposition of Re started with progressive nucleation and two-dimensional growth, followed by two other contributions ... 

After the flame annealing of the noble metal surface at the main chamber, the sample must be transferred to the pre-chamber covered with a droplet of pure water. This reduced the surface contamination by residual atmospheric contaminants. Then, by using the dipping technique [83] that avoids new risks of contamination by the elimination of nitrogen, sulfur, carbon, etc., the surface is put in contact with the solution by careful dipping to avoid water from the lateral side of the hemispherical crystal. The contact of the electrode with the solution is performed potentiostatically at a select potential, where a negligible transient current is observed. This overall experimental process allows the control of surface purity in the system for the electrochemical experiment. This special technique, adopted for the studies on platinum surfaces, provided the novel observations on the behavior of platinum electrodes reported previously [1]. 

As in all potentiostatic techniques, the double layer charging is a parallel process to the faradaic reaction that can substantially attenuate the photocurrent signal at short-time scale (see Section 5.3)" . This element introduces another important difference between fully spectroscopic and electrochemical techniques. Commercially available optical instrumentation can currently deliver time resolution of 50 fs or less for conventional techniques such as transient absorption. On the other hand, the resistance between the two reference electrodes commonly employed in electrochemical measurements at the liquid/liquid interfaces and the interfacial double layer capacitance provide time constants of the order of hundreds of microseconds. Consequently, direct information on the rate of heterogeneous electron injection from/to the excited state is not accessible from photocurrent measurements. These techniques do allow sensitive measurements of the ratio between electron injection and decay of the excited state under pho-tostationary conditions. Other approaches such as photopotential measurements, i.e. relative changes in the Fermi levels in both phases, can provide kinetic information in the nanosecond regime. 

The techniques for characterizing the kinetics of electrode reactions can be classified into steady-state and transient methods. The steady-state methods involve the measurement of the current-potential relationships at constant current (galvanoslatic control) or constant potential (potentiostatic control) conditions and measuring the response, which is either the potential or the current after a steady state is achieved. The non-steady-state methods involve the perturbation of the system from an equilibrium or a steady-state condition, and follow the response of the system as a function of time using current, potential, charge, impedance, or any other accessible property of the interface. Relaxation methods are a subclass of perturbation methods. 

Coulometric titration techniques were used to measure chemical diffusion at between 700 and lOOOC. The transient current response to a potentiostatic step was transformed from the time domain to the frequency domain. The equivalent circuit which was used to fit the resultant impedance data contained an element which described the finite-length diffusion of O into the sample. Other elements which were included were the gas-phase capacitance, and the sum of the gas-phase diffusion resistance and that which was associated with the limited surface exchange kinetics of the sample. The chemical diffusion coefficient of the perovskite, Laq gSrq 2C0O3,... 

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