The basic requirements of a suitable electrolyte for electrochemical devices are high ionic conductivity, low melting and high boiling points, chemical and electrochemical stability, and safety. Electrolyte conductivity and electrochemical stability are key parameters in selecting an electrolyte for modern electrochemical devices such as advanced batteries, fuel cells, super-capacitors, sensors, and electrochromic displays. These parameters, conductivity and electrochemical stability, will receive particular attention in this chapter. Although progress has been made in enhancing the conductivity of solid electrolytes, particularly the polymeric ones, liquid electrolytes are still used in most electrochemical systems. The solvent properties, and dynamics of ion solvent interactions, must be understood in designing new electrolytes. In this chapter, a short but general introduction to properties of solvents and ion-solvent dynamics is discussed.
The history of electrolyte development goes as far back as the work of Greek philosophers in search for a universal solvent, the so-called “Alkahest”. In search of Alkahest, many solvents and chemical rules were discovered such as “like dissolves like” (similia similibus solvuntur) as shown in Table 17.1. Later, the theory of osmotic pressure by van't Hoff (1852–1911), and the theory of electrolyte dissociation by Arrhenius (1859– 1927) were discovered. Many speculations about the nature of solute-solvent interactions and the influence of solvent media on the rate of chemical reaction were proposed in the early eighteen-century. The role of solvents on chemical equilibrium, on tautomerism (i.e. keto-enol tautomerism), and the phenomenon of solvatochromism (shift of UV/Vis absorption bands due to the changes of the index of refraction) were discovered.1,2 Scheibe et al. have correlated the solvating ability of solvents to their degree of influence on reaction rate, chemical equilibrium, and shift in absorption spectra.3
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Nazri, M. (2009). Liquid Electrolytes: Some Theoretical and Practical Aspects. In: Nazri, GA., Pistoia, G. (eds) Lithium Batteries. Springer, Boston, MA. https://doi.org/10.1007/978-0-387-92675-9_17
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