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

Abstract

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-Na_0.612K_0.056MnO₂ 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-Na_0.612K_0.056MnO₂ 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.