Anomalous Sodium Insertion in Highly Oriented Graphite: Thermodynamics, Kinetics and Evidence for Two-Sided Intercalation

TL;DR

This study investigates sodium intercalation into highly oriented graphite, revealing temperature-dependent thermodynamics and kinetics, and provides evidence for two-sided intercalation and unique structural features at different temperatures.

Contribution

It presents detailed thermodynamic, kinetic, and microscopic insights into sodium intercalation in graphite, highlighting temperature effects and two-sided intercalation mechanisms.

Findings

Sodium intercalation requires high temperature for equilibrium.

At high temperature, Na predominantly intercalates in two-sided bilayer form.

Electrochemical insertion benefits from TiO2 coating to reduce resistance.

Abstract

The difficult intercalation of sodium (Na) into graphite is studied by systematic and long-time investigations (of up to 2 years) using highly oriented pyrolytic graphite (HOPG). By studying chemical insertion of solid, liquid and gaseous Na at low and high temperatures (LT, HT) as well as using electrochemical insertion at 25 degree Celsius into uncoated and coated HOPG, it became clear that insertion equilibrium requires HT. On decreasing chemical intercalation temperature from HT (500 degree Celsius) to LT (25 degree Celsius), thermodynamic control was found to change to diffusion control and finally to interfacial control. For the electrochemical insertion, coating (TiO2) proved advisable (to avoid co-intercalation) and efficient in reducing the interfacial resistance. Measured saturation values were found to be not higher than about 1 mol %. Towards room temperature higher equilibrium values cannot be excluded but would in view of the very low driving force kinetically be very difficult to reach. The reversible cell voltage of the saturated composition (versus alkali metal) is distinctly lower than for the analogous cells using lithium (Li) or potassium (K). Detailed transmission electron microscopy (TEM) studies reveal the unexpected fact that at HT Na predominantly enters HOPG in the form of two-sided intercalation sandwiching carbon layers (bilayers), while at LT more highly aggregated layers appear to a comparable degree, accompanied with the formation of higher-dimensional crystal imperfections. The reasons for this peculiar feature and the non-monotonic thermodynamics in the sequence Li-Na-K-Rb-Cs are discussed not only from an energetic but also from an entropic point of view.