Electrodes photoanode

The dye-sensitised solar cell (DSSC) is constructed as a sandwich of two conducting glass electrodes filled with a redox electrolyte. One of the electrodes is coated, using a colloidal preparation of monodispersed TiOj particles, to a depth of a few microns. The layer is heat treated to rednce resistivity and then soaked in a solution of the dye until a monomolecnlar dispersion of the dye on the TiO is obtained. The dye-coated electrode (photoanode) is then placed next to a connter electrode covered with a conducting oxide layer that has been platinised , in order to catalyse the reduction of the mediator. The gap between the two electrodes is filled with an electrolyte containing the mediator, an iodide/triodide conple in acetonitrile. The structure is shown schematically in Fignre 4.29. 

Dye-Sensitized Electrode, Photoanode, Fig. 2 Dye-sensitized solar cell based on mesoporous Ti02 photoanode... 

Dye-Sensitized Electrode, Photoanode Photoelectrochemistry, Fundamentals and Applications... 

In their pioneering work on the formation of photoelectrochemically active metal sulfides by oxidation of the parent metal electrode. Miller and Heller [29] reported the anodic formation of polycrystalline Bi2S3 on a bismuth metal electrode in a sodium polysulfide cell, wherein this electrode was used in situ as photoanode. When a Bi metal electrode is anodized in aqueous sulfide solutions a surface film is formed by the reaction... 

An interesting idea has been to prepare the photosensitive electrode on site having the liquid play the dual role of a medium for anodic film growth on a metal electrode and a potential-determining redox electrolyte in the electrochemical solar cell. Such integration of the preparation process with PEC realization was demonstrated initially by Miller and Heller [86], who showed that photosensitive sulfide layers could be grown on bismuth and cadmium electrodes in solutions of sodium polysulfide and then used in situ as photoanodes driving the... 

Lyden et al. [92] used in situ electrical impedance measurements to investigate the role of disorder in polysulfide PEC with electrodeposited, polycrystalline CdSe photoanodes. Their results were consistent with disorder-dominated percolation conduction and independent of any CdS formed on the anode surface (as verified by measurements in sulfide-free electrolyte). The source of the observed frequency dispersion was located at the polycrystalline electrode/electrolyte interface. 

Diaz AF, Logan JA(1980)Electroactive polyanihne films. JElectroanalChem 111 111-114 Noufi R, Nozik AJ, White J, Warren LF (1982) Enhanced stability of photoelectrodes with electrogenerated polyanUine films. J Electrochem Soc 129 2261-2265 Noufi R, Tench D, Warren LE (1981) Protection of semiconductor photoanodes with photoelectrochemicaUy generated polypyrrole films. J Electrochem Soc 128 2596-2599 Jaeger CD, Fan FRF, Bard AJ (1980) Semiconductor electrodes. 26. Spectral sensitization of semiconductors with phthalocyanine. J Am Chem Soc 102 2592-2598 Gerischer H (1977) On the stability of semiconductor electrodes against photodecomposition. J Electroanal Chem 82 133-143... 

Fujishima A, Sugiyama E, Honda K (1971) Photosensitized electrolytic oxidation of iodide ions on cadmium sulfide single crystal electrode. Bull Chem Soc Japan 44 304 Inoue T, Watanabe T, Fujishima A, Honda K, Kohayakawa K (1977) Suppression of surface dissolution of CdS photoanode by reducing agents. J Electrochem Soc 124 719-722 Elhs AB, Kaiser SW, Wrighton MS (1976) Visible light to electrical energy conversion. Stable cadmium sulfide and cadmium selenide photoelectrodes in aqueous electrolytes. J Am Chem Soc 98 1635-1637... 

The photoanodic dissolution also occurs in the electrochemistry and photoelectrochemistry of compact electrodes of these materials. In fact, it is the most serious obstacle to the practical use of semiconductors such as CdS in photoelectrochemical cells The product of corrosion in the absence of oxygen is sulfur. In the presence of oxygen, sulfate ions are formed as in the case of the colloidal particles... 

Various other semiconductor materials, such as CdSe, MoSe, WSe, and InP were also used in electrochemistry, mainly as n-type photoanodes. Stability against photoanodic corrosion is, naturally, much higher with semiconducting oxides (Ti02, ZnO, SrTi03, BaTi03, W03, etc.). For this reason, they are the most important n-type semiconductors for photoanodes. The semiconducting metal oxide electrodes are discussed in more detail below. 

The photocurrent is cathodic or anodic depending on the sign of the minority charge carriers injected from the semiconductor electrode into the electrolyte, i.e. the n-semiconductor electrode behaves as a photoanode and... 

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