Solar cells electrolyte

Room temperature molten salt systems based on methyl-hexyl-imidazolium iodide appear to afford particular advantages over organic liquids as solvents for solar cell electrolytes. Cell performance showed outstanding stability, with an estimated sensitizer turnover in excess of 50 million (Papageorgiou et al., 1996). 

Figure 15.5 Photocurrent-voltage characteristics of a dye-sensitized solar cell. Electrolyte composition (ionic liquids) 0.9 M ofDMHI-l and30 mM of I2. (acetonitrile) 0.8 M ofDMHI-l, 0.1 M Lil, 50 mM I2, 0.2 M t-butylpyridine. Temperature 25° C. Area 1.0 crrf. AM 1.5 (100 mW cm ) [21]. (Reprinted by permission of the Publisher, The Electrochemical Society of Japan).

Radiation induced redox reactions and the fragmentation of constituent ions in ILs are phenomena which have to be known in detail when using ILs in solar cells, electrolytes etc. Anion fragmentation in ILs starts with radiation induced redox reactions. Scission of the oxidized anions is the main fragmentation pathway, in competition with internal proton transfer reactions involving the aliphatic chains of these anions. Perfluorinated anions show a fluoride loss after a dissociative electron attachment. For example CF3SO3 +e -f CF2S03 is a typical re-... 

The aim of this chapter is to give a state-of-the-art report on the plastic solar cells based on conjugated polymers. Results from other organic solar cells like pristine fullerene cells [7, 8], dye-sensitized liquid electrolyte [9], or solid state polymer electrolyte cells [10], pure dye cells [11, 12], or small molecule cells [13], mostly based on heterojunctions between phthaocyanines and perylenes [14], will not be discussed. Extensive literature exists on the fabrication of solar cells based on small molecular dyes with donor-acceptor systems (see for example [2, 3] and references therein). 

Following the same procedure, the kinetic constants have been determined for very different electrochemical conditions. When n-WSe2 electrodes are compared in contact with different redox systems it is, for example, found9 that no PMC peak is measured in the presence of 0.1 M KI, but a clear peak occurs in presence of 0.1 M K4[Fe(CN)6], which is known to be a less efficient electron donor for this electrode in liquid junction solar cells. When K4[Fe(CN)6] is replaced by K3[Fe(CN)6], its oxidized form, a large shoulder is found, indicating that minority carriers cannot react efficiently at the semiconductor/electrolyte junction (Fig. 31). 

How can such problems be counterbalanced Since a large capacitance of a semiconductor/electrolyte junction will not negatively affect the PMC transient measurement, a large area electrode (nanostructured materials) should be selected to decrease the effective excess charge carrier concentration (excess carriers per surface area) in the interface. PMC transient measurements have been performed at a sensitized nanostructured Ti02 liquidjunction solar cell.40 With a 10-ns laser pulse excitation, only the slow decay processes can be studied. The very fast rise time cannot be resolved, but this should be the aim of picosecond studies. Such experiments are being prepared in our laboratory, but using nanostructured... 

ZnO instead of T1O2 because ZnO provides a 220 times higher mobility for photoinjected electrons, which would allow reduction of the exciting laser intensity. The slow PMC decay of TiOrbased nanostructured sensitization solar cells (the Ru complex as sensitizer), which cannot be matched by a single exponential curve and is influenced by a bias illumination, is strongly affected by the concentration of iodide in the electrolyte (Fig. 38). On the basis of PMC transients and their dependence on the iodide concentration, a kinetic mechanism for the reaction of photoinjected electrons could be elaborated.40... 

Aqueous polysulflde solutions have been widely investigated as primary electrolytes in photoelectrochemical solar cells (PEC Chap. 5). The complexity of these solutions arising from the overlap of multiple chemical equilibria is well... 

Licht S (1995) Electrolyte modified photoelectrochemical solar cells. Sol Energy Mater Sol Cells 38 305-319... 

Electrolyte contacts have been used to characterize as-deposited and annealed CdS/CdTe solar cell structures by photocurrent spectroscopy and electrolyte elec-troabsorbance/electroreflectance measurements (EEA/EER) [267-269]. 

Fig. 5.2 The n-Cd(Se,Te)/aqueous Cs2Sx/SnS solar cell. P, S, and L indicate the direction of electron flow through the photoelectrode, tin electrode, and external load, respectively (a) in an illuminated cell and (b) in the dark. For electrolytes, m represents molal. Electron transfer is driven both through an external load and also into electrochemical storage by reduction of SnS to metaUic tin. In the dark, the potential drop below that of tin sulfide reduction induces spontaneous oxidation of tin and electron flow through the external load. Independent of illumination conditions, electrons are driven through the load in the same direction, ensuring continuous power output. (Reproduced with permission from Macmillan Publishers Ltd [Nature] [60], Copyright 2009)...

It has been illustrated that polycrystalline materials can be operated in regenerative electrolytic solar cells yielding substantial fractions of the respectable energy conversion efficiency obtained by using single crystals. Pressure-sintered electrodes of CdSe subsequently doped with Cd vapor have presented solar conversion efficiencies approaching 3/4 of those exhibited by single-crystal CdSe electrodes in alkaline polysulfide PEC [84]. 

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... 

In any case, it is perceived from the above discussion that the problem of longterm chemical stability of polycrystalline semiconductor liquid junction solar cells is far from being solved. Still, as already pointed out in the early research, any practical photovoltaic and PEC device would have to be based on polycrystalline photoelectrodes. Novel approaches mostly involving specially designed PEC systems with alternative solid or gel electrolytes and, most importantly, hybrid/sensitized electrodes with properties dictated by nanophase structuring - to be discussed at the end of this chapter - promise new advances in the field. 

Licht S, Peramunage D (1990) Efficient photoelectrochemical solar cells from electrolyte modification. Nature 345 330-333... 

Apart from recapture of the injected electrons by the oxidized dye, there are additional loss channels in dye-sensitized solar cells, which involve reduction of triiodide ions in the electrolyte, resulting in dark currents. The Ti02 layer is an interconnected network of nanoparticles with a porous structure. The functionalized dyes penetrate through the porous network and adsorb over Ti02 the surface. However, if the pore size is too small for the dye to penetrate, that part of the surface may still be exposed to the redox mediator whose size is smaller than the dye. Under these circumstances, the redox mediator can collect the injected electron from the Ti02 conduction band, resulting in a dark current (Equation (6)), which can be measured from intensity-modulated experiments and the dark current of the photovoltaic cell. Such dark currents reduce the maximum cell voltage obtainable, and thereby the total efficiency. 

The low efficiencies could be due to lack of intimate contact (interface) between the sensitizer (which is hydrophilic) and the spirobifluorene (which is hydrophobic). Moreover, the surface charge also plays a significant role in the regeneration of the dye by the electrolyte.98 In an effort to reduce the charge of the sensitizer and improve the interfacial properties between the surface-bound sensitizer and the spirobifluorene hole-carrier, amphiphilic heteroleptic ruthenium(II) complexes ((48)-(53)) have been used as sensitizers. These complexes show excellent stability and good interfacial properties with hole-transport materials, resulting in improved efficiencies for the solar cells. 

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