On the Structural Evolution of Pristine P2-Type Na0.67ni0.33mn0.67o2 for Symmetric Full Cell Application

Abstract

P2 type Na0.67Ni0.33Mn0.67O2 (NNMO) is a widely studied layered oxide cathode material for sodium-ion batteries (SIBs) because of its high capacity (160 mAh g-1 practically achieved) and broad voltage window (2V-4.5V). The redox activity in NNMO is shown by both Ni2+ and Mn4+ ions, making it a prospective symmetric SIB electrode material. The average working potential of the symmetric full cell is less due to the limited average working voltages of both the redoxes in a half cell between 2V and 4.5V, resulting in poor energy density. Herein, we report the feasibility of the NNMO symmetric full cell by widening the operational voltage window of NNMO. The electrochemical performance of NNMO half cells between 0.01V and 4V and the structural evolution during cycling are mapped by ex-situ XRD. Na0.44MnO2-like tunnel-type structure (Pbam) with high Na+ content (> 0.90) exists at potentials close to the Mn3+/4+ redox reaction during cycling. The phase change was relatively reversible, implying that the NNMO anode works at such low voltages without the hazard of severe capacity losses. The symmetric full cell made using NNMO cycled between 0.01V and 3V and, at C/10 rate, delivered a capacity of ~68 mAhg- 1.

Keywords: P2 type layered oxide, Symmetric batteries, Hexagonal phase, Tunnel- type structure, orthorhombic phase