Electrodes thin-film control

The analogous voltammograms for a thin-film control electrode containing an essentially identical quantity of TiS2 are shown as the dotted curves... 

The decreased contribution of film resistance for the microtubular electrode makes sense because the effective film thickness for the microtubular system is less than for the thin film control electrode. This is because the surface area of the microtubular current collector is eight times higher than the surface area of the planar current collector. (This factor is calculated from the membrane thickness and the density and diameter of the pores in the membrane.) Since the control and microtubular electrodes contain the same amount of TiS2, the eight times higher underlying surface area of the microtubular electrode means that the TiS2 film is effectively a factor of 8 thinner, relative to the control electrode. 

Figure 3.6 Capacity vs. cycle number for the nanostructured Sn02 and thin-film control electrodes at a charge-discharge rate of 8°C over the potential window of 0.2-0.9 V. Reprinted with permission from Ref. 19.

A number of studies were done in order to determine which of these various factors contribute to the large peak separations observed here. First, it is well known that the effects of resistive elements can be obviated by applying positive feedback [132]. When positive feedback was applied to a thin-film control electrode similar to that described in Fig. 27, the peak separation decreased from —0.8 to —0.35 V (Fig. 28). These data show that resistance does, indeed, contribute to the large AEp values observed here. However, the fact that —0.35 V of this peak splitting cannot be removed by applying positive feedback clearly indicates that slow electron transfer kinetics also contribute to AEj. ... 

The changes in the optical absorption spectra of conducting polymers can be monitored using optoelectrochemical techniques. The optical spectmm of a thin polymer film, mounted on a transparent electrode, such as indium tin oxide (ITO) coated glass, is recorded. The cell is fitted with a counter and reference electrode so that the potential at the polymer-coated electrode can be controlled electrochemically. The absorption spectmm is recorded as a function of electrode potential, and the evolution of the polymer s band stmcture can be observed as it changes from insulating to conducting (11). 

In a similar way, electrochemistry may provide an atomic level control over the deposit, using electric potential (rather than temperature) to restrict deposition of elements. A surface electrochemical reaction limited in this manner is merely underpotential deposition (UPD see Sect. 4.3 for a detailed discussion). In ECALE, thin films of chemical compounds are formed, an atomic layer at a time, by using UPD, in a cycle thus, the formation of a binary compound involves the oxidative UPD of one element and the reductive UPD of another. The potential for the former should be negative of that used for the latter in order for the deposit to remain stable while the other component elements are being deposited. Practically, this sequential deposition is implemented by using a dual bath system or a flow cell, so as to alternately expose an electrode surface to different electrolytes. When conditions are well defined, the electrolytic layers are prone to grow two dimensionally rather than three dimensionally. ECALE requires the definition of precise experimental conditions, such as potentials, reactants, concentration, pH, charge-time, which are strictly dependent on the particular compound one wants to form, and the substrate as well. The problems with this technique are that the electrode is required to be rinsed after each UPD deposition, which may result in loss of potential control, deposit reproducibility problems, and waste of time and solution. Automated deposition systems have been developed as an attempt to overcome these problems. 

Lead sulfide, PbS, nanoparticulate thin films having pancake-like geometry and exhibiting ID quantum confinement, as controlled by the lowest dimension of the particles, have been synthesized by cathodic electrodeposition on TTO/glass and titanium electrodes from a pH 0.62 solution containing Pb(N03)2 and Na2S203 [162]. 

The importance of controlling the operating temperatures of single-crystal and polycrystalline n-CdSe/polysulfide/CoS liquid junction cells to obtain the maximum possible photoconversion has been emphasized [55], In fact, a dramatic effect of temperature was established on the power output of the cells, particularly those based on thin film electrodes. 

FIGURE 10.7 A thin film planar pH microelectrode array with 16 sputtered IrOx electrodes in a 4 X 4 arrangement. The needle type pH electrode as a control can be seen on the upper left comer of the array. (Reproduced from [19], with permission from the Electrochemical Society, Inc.)... 

Water is involved in most of the photodecomposition reactions. Hence, nonaqueous electrolytes such as methanol, ethanol, N,N-d i methyl forma mide, acetonitrile, propylene carbonate, ethylene glycol, tetrahydrofuran, nitromethane, benzonitrile, and molten salts such as A1C13-butyl pyridium chloride are chosen. The efficiency of early cells prepared with nonaqueous solvents such as methanol and acetonitrile were low because of the high resistivity of the electrolyte, limited solubility of the redox species, and poor bulk and surface properties of the semiconductor. Recently, reasonably efficient and fairly stable cells have been prepared with nonaqueous electrolytes with a proper design of the electrolyte redox couple and by careful control of the material and surface properties [7], Results with single-crystal semiconductor electrodes can be obtained from table 2 in Ref. 15. Unfortunately, the efficiencies and stabilities achieved cannot justify the use of singlecrystal materials. Table 2 in Ref. 15 summarizes the results of liquid junction solar cells prepared with polycrystalline and thin-film semiconductors [15]. As can be seen the efficiencies are fair. Thin films provide several advantages over bulk materials. Despite these possibilities, the actual efficiencies of solid-state polycrystalline thin-film PV solar cells exceed those obtained with electrochemical PV cells [22,23]. 

Fig. 3.68. Analytical HPLC chromatograms with detection of diode array of 4.7 x 10"5mol/l of R3R dye curve (1) before and curve (2) after 180 min of photoelectrocatalysis on the Ti02 thin-film electrode biased at +1.0 V in NajSCT, 0.025 mol/l. Curve (4) before and curve (3) after photoelectrocatalysis in NaCl 0.022 mol/l and curve (5) after bleaching of 4.7 X 10-5 mol/l of R3R dye submitted to a chemical treatment by active chlorine addition. The mobile phase was methanol-water 80 20 per cent with a flow rate of 1 ml/min and controlled temperature at 30°C. The column was a Shimpack (Shimadzu) CLC-ODS, 5 /an (250 mm X 4.6 mm). Reprinted with permission from P. A. Cameiro el al. [138].

In the active state, the dissolution of metals proceeds through the anodic transfer of metal ions across the compact electric double layer at the interface between the bare metal and the aqueous solution. In the passive state, the formation of a thin passive oxide film causes the interfadal structure to change from a simple metal/solution interface to a three-phase structure composed of the metal/fUm interface, a thin film layer, and the film/solution interface [Sato, 1976, 1990]. The rate of metal dissolution in the passive state, then, is controlled by the transfer rate of metal ions across the film/solution interface (the dissolution rate of a passive semiconductor oxide film) this rate is a function of the potential across the film/solution interface. Since the potential across the film/solution interface is constant in the stationary state of the passive oxide film (in the state of band edge level pinning), the rate of the film dissolution is independent of the electrode potential in the range of potential of the passive state. In the transpassive state, however, the potential across the film/solution interface becomes dependent on the electrode potential (in the state of Fermi level pinning), and the dissolution of the thin transpassive film depends on the electrode potential as described in Sec. 11.4.2. 

One final issue remains to be resolved Of the portion of the AEpi that is due to resistance, what part is caused by solution resistance and what part is caused by film resistance To explore this issue we examined the electrochemistry of a reversible redox couple (ferrocene/ferricinium) at a polished glassy carbon electrode in the electrolyte used for the TiS 2 electrochemistry. At a peak current density essentially identical to the peak current density for the thin film electrode in Fig. 27 (0.5 mV see ), this reversible redox couple showed a AEpi of 0.32 V (without application of positive feedback). Since this is a reversible couple (no contribution to the peak separation due to slow kinetics) and since there is no film on the electrode (no contribution to the peak separation due to film resistance), the largest portion of this 0.32 V is due to solution resistance. However, the reversible peak separation for a diffusional one-electron redox process is —0.06 V. This analysis indicates that we can anticipate a contribution of 0.32 V -0.06 V = 0.26 V from solution resistance in the 0.5 mV sec control TiS2 voltammogram in Fig. 27. 

This technique yields a catalyst composed entirely of metal nanoparticles or nanocrystalline thin film, and it allows for control of size and distribution while eliminating the need for a dispersing and supporting medium. The obtained electrodes contained as little as 0.017 mg Pt/cm and performed as well as standard E-TEK electrodes (Pt loading 0.4 mg/cm ). The PLD technique may be of special interest as an alternative to the sputtering process in the production of micro fuel cells. 

Interest has developed in electrochromic light transmission modulators, which are called smart windows , for control of temperature and lighting in buildings and automobiles. A cross section of an electrochromic light transmission modulator is shown in Fig. 11.31 (Rauh and Cogan, 1988). The two electrochromic elements of the structure are designated ECl and EC2, and are sandwiched between two thin film, optically transparent, electrodes of ITO and separated by an electrolyte. The ECl layer should colour when a negative potential is applied and the EC2 layer should either colour under positive potentials or remain in a transparent state. This is indicated by the chemical reactions ... 

Without doubt, the advent of carbon nanotubes has opened up iimovative perspectives for research and development of carbon electrodes. In this chapter, we have attempted to highlight the electrochemical properties of carbon nanotubes by rooting them mainly on their structural, electronic and chemical properties. If chirality of SWNTs could be controlled, it would be possible to probe electrochemically the unique electronic properties of the tubes with their corresponding unique DOS distribution and establish direct correlations between electronic structure and electrochemistry. However, so far, most of their electrochemical applications are based on ensembles of CNTs (MWNTs or SWNTs) in thin films supported on conductive surfaces or composites. Such ensembles, not so well defined from the structural point of view, contain a mixture of tubes with different diameters and DOS... 

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