Tuning local chemistry of P2 layered-oxide cathode for high energy and long cycles of sodium-ion battery.

Layered transition-metal oxides have attracted intensive interest for cathode materials of sodium-ion batteries. However, they are hindered by the limited capacity and inferior phase transition due to the gliding of transition-metal layers upon Na+ extraction and insertion in the cathode materials. Here, we report that the large-sized K+ is riveted in the prismatic Na+ sites of P2-Na0.612K0.056MnO2 to enable more thermodynamically favorable Na+ vacancies. The Mn-O bonds are reinforced to reduce phase transition during charge and discharge. 0.901 Na+ per formula are reversibly extracted and inserted, in which only the two-phase transition of P2 ↔ P’2 occurs at low voltages. It exhibits the highest specific capacity of 240.5 mAh g−1 and energy density of 654 Wh kg−1 based on the redox of Mn3+/Mn4+, and a capacity retention of 98.2% after 100 cycles. This investigation will shed lights on the tuneable chemical environments of transition-metal oxides for advanced cathode materials and promote the development of sodium-ion batteries. High-capacity and structural stable cathode materials are challenges for sodium-ion batteries. Here, the authors report a layered P2-Na0.612K0.056MnO2 with large-sized K+ riveted in the Na-layers to enable 0.9 Na+ (de)insertion with a reversible phase transition of P2-P’2.