Layered Na‐Ion Cathodes with Outstanding Performance Resulting from the Synergetic Effect of Mixed P‐ and O‐Type Phases

Abstract

Herein, the synthesis of new quaternary layered Na-based oxides of the type Na <i>_x</i> Mn <i>_y</i> Ni <i>_z</i> Fe_0.1Mg_0.1O₂ (0.67≤ <i>x</i> ≤ 1.0; 0.5≤ <i>y</i> ≤ 0.7; 0.1≤ <i>z</i> ≤ 0.3) is described. The synthesis can be tuned to obtain P2- and O3-type as well as mixed P-/O-type phases as demonstrated by structural, morphological, and electrochemical properties characterization. Although all materials show good electrochemical performance, the simultaneous presence of the P- and O-type phases is found to have a synergetic effect resulting in outstanding performance of the mixed phase material as a sodium-ion cathode. The mixed P3/P2/O3-type material, having an average elemental composition of Na_0.76Mn_0.5Ni_0.3Fe_0.1Mg_0.1O₂, overcomes the specific drawbacks associated with the P2- and O3-type materials, allowing the outstanding electrochemical performance. In detail, the mixed phase material is able to deliver specific discharge capacities of up to 155 mAh g^-1 (18 mA g^-1) in the potential range of 2.0-4.3 V. In the narrower potential range of 2.5-4.3 V the material exhibits high average discharge potential (3.4 V versus Na/Na⁺), exceptional average coulombic efficiencies (>99.9%), and extraordinary capacity retention (90.2% after 601 cycles). The unexplored class of P-/O-type mixed phases introduces new perspectives for the development of layered positive electrode materials and powerful Na-ion batteries.