Abstract
AbstractThe relationship between structure and ion transport in liquid electrolyte solutions is not well understood over the whole concentration and temperature ranges. In this work, we have studied the ionic conductivity (κ) as a function of molar fraction (x) and Temperature (T) for aqueous solutions of salts with nitrate anion and different cations (proton, lithium, calcium, and ammonium) along with their liquid-solid phase diagrams. The connection between the known features in the phase diagrams and the ionic conductivity isotherms is established with an insight on the conductivity mechanism. Also, known isothermal (κ vs.. x) and iso-compositional (κ vs.. T) equations along with a proposed two variables semi-empirical model (κ = f (x, T)) were fitted to the collected data to validate their accuracy. The role of activation energy and free volume in controlling ionic conductivity is discussed. This work brings us closer to the development of a phenomenological model to describe the structure and transport in liquid electrolyte solutions.
Funder
Gouvernement du Canada | Ressources naturelles Canada | Office of Energy Research and Development
Funding information The authors thank the Office of Energy Research and Development at Natural Resources Canada for financial support.
Publisher
Springer Science and Business Media LLC
Subject
Materials Chemistry,Biochemistry,Environmental Chemistry,General Chemistry
Reference30 articles.
1. Barthel, J. M. G., Krienke, H. & Kunz, W. Physical Chemistry of Electrolyte Solutions: Modern Aspects. (Springer, Berlin, 1998).
2. Smart, M. C. et al. The structure of electrolyte solutions. Reports Prog. Phys. 44, 593 (1981).
3. Angell, C. A. & Bressel, R. D. Fluidity and conductance in aqueous electrolyte solutions. An approach from the glassy state and high-concentration limit. I. Ca(NO3)2 solutions. J. Phys. Chem. 76, 3244–3253 (1972).
4. Smedley, S. I. The Interpretation of Ionic Conductivity in Liquids. (Plenum Press, New York, 1980).
5. Yamada, Y. & Yamada, A. Review—Superconcentrated Electrolytes for Lithium Batteries. J. Electrochem. Soc. 162, A2406–A2423 (2015).