Bulk properties, liquid electrolytes

Due to the core importance of the SEI formation on carbonaceous anodes, the majority of the research activities on additives thus far aim at controlling the chemistry of the anode/electrolyte interface, although the number of publications related to this topic is rather limited as compared with the actual scale of interest by the industry. Table 9 summarizes the additives that have been described in the open literature. In most cases, the concentration of these interface-targeted additives is expected to be kept at a minimum so that the bulk properties of the electrolytes such as ion conduction and liquid ranges would not be discernibly affected. In other words, for an ideal anode additive, its trace presence should be sufficient to decouple the interfacial from bulk properties. Since there is no official standard available concerning the upper limit on the additive concentration, the current review will use an arbitrary criterion of 10% by weight or volume, above which the added component will be treated as a cosolvent instead of an additive. 

Subject areas for the Series include solutions of electrolytes, liquid mixtures, chemical equilibria in solution, acid-base equilibria, vapour-liquid equilibria, liquid-liquid equilibria, solid-liquid equilibria, equilibria in analytical chemistry, dissolution of gases in liquids, dissolution and precipitation, solubility in cryogenic solvents, molten salt systems, solubility measurement techniques, solid solutions, reactions within the solid phase, ion transport reactions away from the interface (i.e. in homogeneous, bulk systems), liquid crystalline systems, solutions of macrocyclic compounds (including macrocyclic electrolytes), polymer systems, molecular dynamic simulations, structural chemistry of liquids and solutions, predictive techniques for properties of solutions, complex and multi-component solutions applications, of solution chemistry to materials and metallurgy (oxide solutions, alloys, mattes etc.), medical aspects of solubility, and environmental issues involving solution phenomena and homogeneous component phenomena. 

The development of photocathode materials for either single- or dual-absorber cells has also received considerable attention [80, 101, 102]. Thermodynamic equilibrium dictates that p-type semiconductors will exhibit upward band bending when in contact with a liquid electrolyte. This behaviour is the opposite to that of n-type semiconductors described previously, and will result in the movement of photogenerated electrons towards the semiconductor-electrolyte interface while the holes are driven into the bulk of the electrode, towards the electrical back contact. At the surface, provided that the energy carried by the electrons is sufficient, H2 is evolved. As discussed previously, one of the electronic properties of metal oxides that makes them suitable for water photo-oxidation purposes is the O 2p character of the valence electrons, which places the VB edge at potentials... 

A bulk ionic liquid can be considered as a pure electrolyte (Rogers Seddon, 2005a). It is made entirely of molecular ions and besides its actual composition or the actual nature of the molecular ions that it is made of, many of the appealing properties which have been exploited in the technological applications are due to this feature. 

Since bulk properties, of either solid or liquid phases, clearly are not always appropriate to describe these reactions and molecular states at electrode/electrolyte phase boundaries, it is evident that these unique systems require innovative spectroscopic techniques and theoretical advancements to enable us to understand fully the origins of their spectra. Development of in situ techniques is especially important because crystalline electrode surfaces can restructure when removed from an electrolyte to vacuo, e.g.. Ref. 1, or by... 

The bulk properties of water and of solutions of electrolytes in water have been reviewed by VON Erichsen [1955]. Furthermore, the theory of ionic solution was the theme of a discussion sponsored and published by the Faraday Society [1957]. An account of the more recent literature is contained in a review on clay-water relationships by Graham [1964] and in an article by Luck [1964]. Therefore, the treatment in this chapter will be limited to the effects of the solid interface in soils and clays on the properties of the liquid phase in the vicinity of the solid surface. 

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 characteristic effect of surfactants is their ability to adsorb onto surfaces and to modify the surface properties. Both at gas/liquid and at liquid/liquid interfaces, this leads to a reduction of the surface tension and the interfacial tension, respectively. Generally, nonionic surfactants have a lower surface tension than ionic surfactants for the same alkyl chain length and concentration. The reason for this is the repulsive interaction of ionic surfactants within the charged adsorption layer which leads to a lower surface coverage than for the non-ionic surfactants. In detergent formulations, this repulsive interaction can be reduced by the presence of electrolytes which compress the electrical double layer and therefore increase the adsorption density of the anionic surfactants. Beyond a certain concentration, termed the critical micelle concentration (cmc), the formation of thermodynamically stable micellar aggregates can be observed in the bulk phase. These micelles are thermodynamically stable and in equilibrium with the monomers in the solution. They are characteristic of the ability of surfactants to solubilise hydrophobic substances. 

Thin layer — A layer of -+ electrolyte solution (molten salt electrolyte, - ionic liquid) of about 2 to 100 pm thickness is commonly treated as a thin layer because of particular properties and behavior. In bulk - electrolysis methods the amount of convertible species contained in a thin layer is very limited, thus exhaustive electrolysis becomes feasible. In numerous spectroelec-trochemical setups the electrolyte solution confined between the electrode surface under investigation and the... 

Any inference concerning the effects of a possibly altered molecular structure of water near the solid surfaces in soil clays must proceed from an acquaintance with the structure of liquid water in bulk and in aqueous electrolyte solutions. In this section, the current picture of the molecular arrangement in bulk water is reviewed. In Sec. 2.2, the same is done for aqueous solutions of inorganic electrolytes. These summaries are followed by discussions of the structure of water near the surfaces of phyllosilicates and the effect of these surfaces on the solvent properties of the water molecule. 

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