Substantial Na-Ion Storage at High Current Rates: Redox-Pseudocapacitance through Sodium Oxide Formation.

Abstract

Batteries and supercapacitors, both governed by electrochemical processes, operate by different electrochemical mechanisms which determine their characteristic energy and power densities. Battery materials store large amounts of energy by ion intercalation. Electrical double-layer capacitors store charge through surface-controlled ion adsorption which leads to high power and rapid charging, but much smaller amounts of energy stored. Pseudocapacitive materials offer the promise to combine these properties by storing charge through surface-controlled, battery-like redox reactions but at high rates approaching those of electrochemical double-layer capacitors. This work compares the pseudo-capacitive charge storage characteristics of self-organized titanium dioxide (TiO2-x) nanotubes (NTs) to flat TiO2-x surface films to further elucidate the proposed charge storage mechanism within the formed surface films. By comparing TiO2-x NTs to flat TiO2-x surface films, having distinctively different oxide mass and surface area ratios, it is shown that NaO2 and Na2O2 formation, which constitutes the active surface film material, is governed by the metal oxide bulk. Our results corroborate that oxygen diffusion from the lattice oxide is key to NaO2 and Na2O2 formation.