Viscosity liquid electrolytes

Of course these requirements cannot be fulfilled simultaneously. For example, a low vapor pressure of the liquid electrolyte is obtained only by using more viscous dipolar aprotic solvents such as propylene carbonate, but high solvent viscosity generally entails a low conductivity. Nevertheless, a large number of useful solvents and electrolytes is available, allowing a sufficiently good approximation to an ideal electrolyte. 

Flow of the liquid past the electrode is found in electrochemical cells where a liquid electrolyte is agitated with a stirrer or by pumping. The character of liquid flow near a solid wall depends on the flow velocity v, on the characteristic length L of the solid, and on the kinematic viscosity (which is the ratio of the usual rheological viscosity q and the liquid s density p). A convenient criterion is the dimensionless parameter Re = vLN, called the Reynolds number. The flow is laminar when this number is smaller than some critical value (which is about 10 for rough surfaces and about 10 for smooth surfaces) in this case the liquid moves in the form of layers parallel to the surface. At high Reynolds numbers (high flow velocities) the motion becomes turbulent and eddies develop at random in the flow. We shall only be concerned with laminar flow of the liquid. 

A lithium ion transference number significantly less than 1 is certainly an undesired property, because the resultant overwhelming anion movement and enrichment near electrode surfaces would cause concentration polarization during battery operation, especially when the local viscosity is high (such as in polymer electrolytes), and extra impedance to the ion transport would occur as a consequence at the interfaces. Fortunately, in liquid electrolytes, this polarization factor is not seriously pronounced. 

The calculation of viscosities of electrolyte mixtures can be accomplished with the method of Andrade (see Ref. [40]) extended with the electrolyte correction by Jones-Dole [44]. First, the pure component viscosities of molecular species are determined by the three-parametric Andrade equation, which allows a mixing rule to be applied and the mixture viscosity of an electrolyte-free liquid phase to be obtained. The latter is transformed into the viscosity of the liquid phase using the electrolyte correction term of Jones and Dole [44], whereas the ionic mobility and conductivity are used as model parameters. 

An appreciation of the properties of liquid electrolytes can be gained by a comparison between molten ice (water) and molten sodium chloride (Table 5.2). Both liquids are clear and colorless. Their viscosities, thermal conductivities, and surface tensions near their melting points are not very different. 

Marcus Y (2005a) BET nodehng of solid-liquid phase diagrams of common ion binary stilt hydrate mixtures. 1. The BET parameters. J Sol Chem 34 297-306 Marcus Y (2006) On the molar volumes and viscosities of electrolytes. J Sol Chem 35 1271-1286 Marcus Y (2007) Gibbs energies of transfer of anions from water to mixed aqueous organic solvents. Chem Rev 107 3880-3897... 

FIGURE 2.70 Cyclic voltammograms for [EMIMllBFJ at 5 mV s" . (Sillars, F. B. et al. 2012. Variation of electrochemical capacitor performance with room temperature ionic liquid electrolyte viscosity and ion size. Physical Chemistry Chemical Physics 14 6094-6100. Reproduced by permission of The Royal Society of Chemistry.)... 

Mayrand-Provencher, L., and D. Rochefort. 2009. Influence of the conductivity and viscosity of protic ionic liquids electrolytes on the pseudocapacitance of RuOj electrodes. Journal of Physical Chemistry C 113 1632-1639. 

Indeed, one matter of concern in the development of new polymer ionic membranes lies in the fact that their high conductivity is often associated with amorphous, low-viscosity phases. Therefore, in their conductive form, these membranes behave like soft solids with poor mechanical stability their direct use in LPBs may give rise to those problems commonly met in conventional liquid electrolyte systems, such as leakage, loss of interfacial contacts and short circuits. Under these circumstances, one of the most useful feature of LPBs, namely the solid-state configuration, would then be lost. Consequently, it is of key importance to assure that the polymer electrolyte membrane maintains good mechanical properties even in its conductive state. 

Carbonate-containing liquid electrolytes are primarily chosen for their ability to dissolve lithium salts and their relatively low viscosity (which facilitates Li-ion diffusion between electrodes). Their flammability has in part led to interest in the use of room-temperature ionic liquids (ILs) as replacements. ILs can potentially operate in a higher voltage window relative to carbonates and also have the added benefit of being more thermally stable and having low vapor pressure. The main drawback of this class of compounds is a high viscosity. Additionally, carbonates may have to be introduced at certain voltages to form a suitable SEI for operation. 

The number of studies which utilize ionic liquid electrol54e in redox capacitor system is still small, probably due to the difficulty to reproduce the pseudo-capacitive reaction in ionic liquid media. While the principle of pseudo-capacitance of conductive polymer electrodes permits to utilize ionic liquid electrolytes, high viscosity and rather inactive ions of ionic liquid may make their pseudo-capacitive reaction slow. The combination of nanostmctured conductive polymer electrode and ionic liquid electrolyte is expected to be effective [27]. It is far difficult that ionic liquids are utilized in transition metal-based redox capacitors where proton frequently participates in the reaction mechanisms. Some anions such as thiocyanate have been reported to provide pseudo-capacitance of manganese oxide [28]. The pseudo-capacitance of hydrous ruthenium oxide is based on the adsorption of proton on the electrode surface and thus requires proton in electrolyte. Therefore ionic liquids having proton have been attempted to be utilized with ruthenium oxide electrode [29]. Recent report that 1,3-substituted imidazolium cations such as EMI promote pseudo-capacitive reaction of mthenium oxide is interesting on the viewpoint of the establishment of the pseudo-capacitive system based on chemical nature of ionic liquids [30]. 

In some cases hydrogels or an electrolyte inside a porous matrix are used to replace free liquid electrolytes to raise viscosity, lower evaporation rates, and resist leakage of the electrolyte from sensor devices. The polymers or hydrogels can prevent the evaporation of electrolyte during sensor fabrication, especially for microsensor devices where very small amounts of electrolyte are used (Stetter and Li 2008). 

For liquid electrolytes, ionic conductivity, self-diffusivity, and viscosity are three key properties. Though originally based on dilute aqueous electrolyte solutions, the Walden rule [52] has been proposed as a tool to provide insight to the proton transfer and ion association. The rule suggests that the molar cmiductivity of an electrolyte, A, is proportional to the fluidity, which can be expressed as the inverse of the shear viscosity i/. In other words, the product of the molar conductivity and viscosity of an electrolyte is a constant, as shown in (3.10). 

After the electroviscous effect was discovered in pure liquids, many solutions containing simple electrolytes were comprehensively investigated. Note that there is no an external electric field applied to the electrolyte systems, as most of such systems are aqueous solutions, which arc unable to afford for a high electric field. Poiscuilic [95] was the first to observe that the viscosity of electrolytic solutions differs from that of the solvents. Further work was carried out by Jones [96], and Falkenhagen [97]. It was found that the electroviscous effect of an electrolyte solution is much stronger than the effect observed in the pure liquids. According to Jones [98], the viscosity of an electrolytic solution can be represented as ... 

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