Murdoch University Research Repository

Welcome to the Murdoch University Research Repository

The Murdoch University Research Repository is an open access digital collection of research
created by Murdoch University staff, researchers and postgraduate students.

Learn more

Ion solvation in lithium battery electrolyte solutions. 1. Apparent molar volumes

Atkins, P., Hefter, G.T. and Singh, P. (1991) Ion solvation in lithium battery electrolyte solutions. 1. Apparent molar volumes. Journal of Solution Chemistry, 20 (11). pp. 1059-1078.

Link to Published Version:
*Subscription may be required


Apparent molar volumes, Vφ{symbol}(MX), of seven electrolytes (NaClO4, NaCF3SO3, NaBPh4, LiClO4, LiAsF6, Ph4AsCF3SO3 and KCF3SO3) have been determined by vibrating-tube densimetry in nonaqueous solvent mixtures of propylene carbonate (PC) with acetonitrile (AN), dimethoxyethane (DME) and tetrahydrofuran (THF). Vφ{symbol}(MX) was measured at an electrolyte concentration of 0.05M over the entire solvent composition range wherever possible. Ionic apparent molar volumes of transfer, ΔtV φ(ion), were obtained via the tetraphenylarsonium tetraphenylborate (TATB) assumption. ΔtV φ(ion) from PC to the mixed solvents are generally strongly negative for both cations and anions consistent with the greater compressibilities and lower dielectric constants of the cosolvents. In PC/AN mixtures cations and anions have similar values of ΔtV φ(ion) but in PC/DME and PC/THF mixtures they differ considerably. Cationic volumes show the expected dependence on ion-size but the differences among the anion volumes are much greater than expected at high cosolvent compositions. These effects are discussed in terms of preferential solvation and other solvent interactions. The implications of these findings for lithium batteries are briefly discussed.

Item Type: Journal Article
Murdoch Affiliation(s): School of Mathematical and Physical Sciences
Publisher: Springer Netherlands
Copyright: © Plenum Publishing Comporation
Item Control Page Item Control Page