Study of Ion Transport in Lithium Perchlorate-Succinonitrile Plastic Crystalline Electrolyte via Ionic Conductivity and in Situ Cryo-Crystallography

• Published in: The journal of physical chemistry. B 2009-04, Vol.113 (15), p.5025-5031
• Main Authors: Das, Supti, Prathapa, Siriyara J, Menezes, Pramod V, Row, Tayur N. Guru, Bhattacharyya, Aninda J
• Format: Article
• Language: English
• Subjects: B: Macromolecules, Soft Matter; Calorimetry, Differential Scanning; Crystallography, X-Ray; Electric Conductivity; Electrolytes - chemistry; Ion Transport; Lithium Compounds - chemistry; Magnetic Resonance Spectroscopy; Models, Molecular; Nitriles - chemistry; Perchlorates - chemistry; Spectroscopy, Fourier Transform Infrared; Temperature
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp809465u

Ion transport mechanism in lithium perchlorate (LiClO4)-succinonitrile (SN), a prototype of plastic crystalline soft matter electrolyte is discussed in the context of solvent configurational isomerism and ion solvation. Contributions of both solvent configurational isomerism and ion solvation are reflected in the activation energy for ion conduction in 0−1 M LiClO4−SN samples. Activation energy due to solvent configurational changes, that is, trans−gauche isomerism is observed to be a function of salt content and decreases in presence of salt (except at high salt concentrations, e.g. 1 M LiClO4−SN). The remnant contribution to activation energy is attributed to ion-association. The X-ray diffraction of single crystals obtained using in situ cryo-crystallography confirms directly the observations of the ionic conductivity measurements. Fourier transform infrared spectroscopy and NMR line width measurements provide additional support to our proposition of ion transport in the prototype plastic crystalline electrolyte.