Pseudocapacitive charge storage properties of Na2/3Co2/3Mn2/9Ni1/9O2 in Na-ion batteries

The behaviour of Na2/3Co2/3Mn2/9Ni1/9O2 in composite electrodes is studied via Na half-cells utilizing a dedicated cyclic voltammetry approach. The application of increasing sweep rates enabled a detailed analysis of the red-ox peaks of this material. All peak currents due to cathodic/anodic processes demonstrated clear capacitive properties. This finding widens the picture of classical Na+ insertion/ extraction in this complex oxide, as purely diffusive processes of Na+ through its layers do not fully explain the pseudocapacitance displayed by its red-ox peaks, which are typically linked to concomitant oxidation state changes for its transition metal atoms and/or phase transitions. No phase transition was observed during in operando X-Ray diffraction upon charge to 4.2 V vs. Na+/Na, proving good structural stability for P2-NaxCo2/3Mn2/9Ni1/9O2 upon Na+ removal. The origin of such pseudocapacitive properties is likely nested in strong electrostatic interactions among the metal oxide slabs and a tendency to release Na+ from its crystallites, e.g. to form surface by-products upon air exposure. Such a reactivity induces defects (e.g. vacancies) in its lattice and charge compensation mechanisms are required to maintain an overall charge neutrality, thus ultimately influencing the electrochemical properties. Possible limiting factors for the performances of this compound in composite coatings are also discussed. (C) 2018 The Authors. Published by Elsevier Ltd.