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

Abstract

Ion transport mechanism in lithium perchlorate (LiClO(4))-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 LiClO(4)-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 LiClO(4)-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.

Ceramic and polymeric solid electrolytes for lithium-ion batteries

“…20 [206,[209][210][211][212][213][214]. The PAN-based electrolytes with the best conductivities are those with a LiClO 4 salt and SN, the conductivity of which is included for comparison.…”

In Situ Synthesis of a Hierarchical All‐Solid‐State Electrolyte Based on Nitrile Materials for High‐Performance Lithium‐Ion Batteries

“…Generally, two types of behavior for the ionic conductivity of electrolyte are reported in the literature. The fi rst behavior is described by the Arrhenius equation, which is related to the ion hopping decoupled from long-range motions of the matrix [ 32 ] …”

Increasing ionic conductivity of polymer–sodium salt complex by addition of a non-ionic plastic crystal

“…Depending on the salt type and concentration, SNbased plastic electrolytes have been observed to show very high ambient temperature ionic conductivity ∼ 10 − 4 -10 − 2 Ω − 1 cm − 1 in the plastic phase temperature range of SN. The high ionic conductivity has been attributed to the trans-gauche isomerism [7,8,17] of the plastic crystal molecule which enhances the mobility of the mobile ion species. In Ref.…”