Solar cells, redox reactions

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]. 

The diffusion length of photogenerated charge carriers is one of the important parameters governing the efficiency of a solar cell. In conventional cells, this is an intrinsic property of the semiconductor and its purity [34]. However, in DSSCs, the diffusion length is a function of the rate of reaction (4) and, thus, varies with different redox couples, surface treatments, and so forth. When the oxidation of R [reaction (2)] is chemically irreversible, the diffusion length of electrons is effectively infinite, whereas with kinetically fast, reversible redox couples (see Section VI), it approaches zero with unpassivated interfaces. 

The rate of electron transport in dye-sensitized solar cells is a major element of the overall efficiency of the cells. The injected electrons into the conduction band, from optically excited dye, can traverse the Ti(>2 network and can be collected at the transparent conducting glass or can react either with oxidized dye molecule or with the oxidized redox couple (recombination). The reaction of injected electrons into the conduction band with the oxidized redox mediator gives undesirable dark currents, reducing significantly the charge-collection efficiency, and thereby decreasing the total efficiency of the cell (Fig. 7). 

Other parameters that need to be considered to achieve efficient dye-sensitized solar cells include the open circuit photovoltage, Voc, which is determined theoretically by the potential difference between the Fermi level of the semiconductor and the Nernst potential of the redox couple in solution, i.e. I-/l3- in the case of the cell under consideration here. However, there are kinetic reasons why the theoretical value is not obtained in practice. One issue to be considered, for example, is the energy-wasting reaction of a recombination of the injected electrons with the I3-produced upon reduction of the oxidized dye. 

This is considerably different from the recombination reaction with, for example, typical ruthenium dyes. This slow re-reduction of the dyad is explained by the low redox potential of the osmium center, the value of 0.66 V (vs. SCE) observed, points to a small driving force for the redox process. This observation is important for the design of dyes for solar cell applications. Osmium compounds have very attractive absorption features, which cover a large part of the solar spectrum. However, their much less positive metal-based oxidation potentials will result in a less effective re-reduction of the dyes based on that metal and this will seriously affect the efficiency of solar cells. In addition, for many ruthenium-based dyes, the presence of low energy absorptions, desirable for spectral coverage, is often connected with low metal-based redox potentials. This intrinsically hinders the search for dyes which have a more complete coverage of the solar spectrum. Since electronic and electrochemical properties are very much related, a lowering of the LUMO-HOMO distance also leads to a less positive oxidation potential. 

Iodine — Iodine, L, is a halogen which occurs naturally mainly as iodide, I- [i]. Iodine (Greek ioeides for colored violet ) is a black solid with a melting point of 113.6 °C which is readily undergoing sublimation to form a violet gas. Iodine occurs in the oxidation states -1,0, +1, +3, +5, +7 and it possesses a rich redox chemistry [ii]. In aqueous solution the formation of I2 from I- occurs with a standard potential of 0.621V vs. SHE and this oxidation process is preceded by the formation of I3 with a standard potential of 0.536 V vs. SHE. For the reaction I2(cryst) + 2e - 21 E = 0.535 V. The I—/I3 redox couple is employed, for example, in solar cells [iii] and in long-lived lithium-iodine battery systems. The oxidation of I2 in organic solvents results formally in I+ intermediates which is a powerful oxidant and useful, for example, in electro-synthetic chemical processes [ii]. 

Figure 1.8 Cell schematics for a regenerative solar cell based on (a) an n-type photoelectrode (b) ap-type photoelectrode. The top diagrams show the cell reactions under illumination, the middle diagrams the electronic energy levels and band bending, and the bottom diagrams the cell current-voltage (I-U) characteristics with the photoelectrode and counter electrode (CE) currents shown in the same quadrant. The maximum power point is located at the point on the current-voltage curve at which the rectangle of maximum area may be inscribed in this quadrant. The photovoltage V, the electron and hole quasi-Fermi levels E and fip and the solution Fermi level f o.R, the open-circuit potential Ugc of the photoelectrode and the standard redox potential 17 ° of the 0,R redox couple are also shown.

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