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Comparative Study of Alkali-Cation-Based (Li+ , Na+ , K+ ) Electrolytes in Acetonitrile and Alkylcarbonates.

Chemphyschem : a European journal of chemical physics and physical chemistry (2019-01-08)
Samia Amara, Joël Toulc'Hoat, Laure Timperman, Agnès Biller, Hervé Galiano, Corinne Marcel, Matthieu Ledigabel, Mérièm Anouti
ABSTRACT

The development of a suitable functional electrolyte is urgently required for fast-charging and high-voltage alkali-ion (Li, Na, K) batteries as well as next-generation hybrids supercapacitors. Many recent works focused on an optimal selection of electrolytes for alkali-ion based systems and their electrochemical performance but the understanding of the fundamental aspect that explains their different behaviour is rare. Herein, we report a comparative study of transport properties for LiPF6 , NaPF6 , KPF6 in acetonitrile (AN) and a binary mixture of ethylene carbonate (EC), dimethyl carbonate (DMC): (EC/DMC : 1/1, weigh) through conductivities, densities and viscosities measurements in wide temperature domain. By application of the Stokes-Einstein, Nernst-Einstein, and Jones Dole equations, the effective ionic solvated radius of cation (reff ), the ionic dissociation coefficient (αD ) and structuring Jones Dole's parameters (A, B) for salt are calculated and discussed according to solvent or cation nature as a function of temperature. From the results, we demonstrate that better mobility of potassium can be explained by the nature of the ion-ion and ion-solvent interactions due to its polarizability. In the same time, the predominance of triple ions in the case of K+ , is a disadvantage at high concentration.