Slope-structure design towards high-stability P2-Na0.67MnO2 cathode

Abstract

Layered Mn-based oxide P2-Na0.67MnO2 (NMO) arouses enormous interest for its high specific capacity, easy preparation and low cost. Meanwhile, the P2 → O2 phase transition derived from the slippage of transition metal (TM) layer leads to the inferior performance. Herein, we design a co-doping into Na+ (102 pm) lattice site with smaller-sized Li+ (76 pm) and larger-sized K+ (138 pm) to construct a slope-structured P2-Na0.63K0.02Li0.02MnO2 (NKLMO). The anchored Li+ and K+ can serve as pillar effects and form a geometrically stable resembling triangular structure in the Na-interlayer. Moreover, such a slope-structure is clearly verified by the HRTEM images. In-situ XRD and in-situ EIS tests efficaciously clarify the improved structural stability and even lower impedance during cycling within 2.0–4.2 V, respectively. DFT calculations further confirm the stronger metallicity of NKLMO electrode than the bare NMO originated from the more mobile free electrons surrounding the vicinity of Fermi level. By grace of the more stable slope-structure and faster reaction kinetics, NKLMO is capable of displaying high initial capacity (206.5 mA h/g) and energy density (540 W h kg−1), with a competitive cycling stability at both low and high current rates (96 %@100 cycles@0.1C; 88.4 %@500 cycles@5C). This slope-design is above rubies for tuning chemistry environment to exploit high-stability P2-phase cathodes for sodium-ion batteries.