Experimental and Theoretical Investigation of the Ion Conduction Mechanism of Tris(adiponitrile)perchloratosodium, a Self-Binding, Melt-Castable Crystalline Sodium Electrolyte

Abstract

Sodium perchlorate (NaClO4) crystallizes with adiponitrile (ADN) as a 1:3 solvate to produce (ADN)(3) NaClO4, a solid electrolyte for sodium ion conduction. The solid possesses high thermal stability (up to 150 degrees C) and the ability to be melt-cast (T-m = 81 degrees C). The pressed solid has a high ionic conductivity of 2.2 x 10(-4) S cm(-1) at room temperature with a low activation barrier for ion conduction of 22 kJ mol(-1). The high conductivity is the result of low-affinity ion-conduction channels in the bulk based on the X-ray crystal structure, and by low grain-boundary resistance and possibly a grain-boundary percolating network due to a fluidlike nanoliquid layer between the grains, observable by scanning electron microscopy and differential scanning calorimetry. When the liquid nanolayer is rinsed away or removed by excessive drying, the bulk room temperature ionic conductivity is 4 x 10(-5) S cm(-1), activation energy for ionic conduction for an organic solid is 37 kJ mol(-1), and the sodium ion transference number is 0.71. Scanning electron microscopy and classical molecular dynamics simulations suggest that these cocrystals form a fluid layer of ADN at the surface, which facilitates the Na+ ion migration between the grains. Density functional theory calculations are consistent with the possibility of ion conduction via a solvent-anion coordinated transition state through vacancy defects in the three symmetry-equivalent ion channels along separate directions, suggesting the possibility of ionic conductivity in three dimensions.