A P3-Type K_1/2Mn_5/6Mg_1/12Ni_1/12O₂ Cathode Material for Potassium-Ion Batteries with High Structural Reversibility...

Mn-based layered oxides are very attractive as cathodes for potassium-ion batteries (PIBs) due to their low-cost and environmentally friendly precursors. Their transfer to practical application, however, is inhibited by some issues including consecutive phase transitions, sluggish K⁺ deintercalation/intercalation, and serious capacity loss. Herein, Mg-Ni co-substituted K_1/2Mn_5/6Mg_1/12Ni_1/12O₂ is designed as a promising cathode material for PIBs, with suppressed phase transitions that occurred in K_1/2MnO₂ and improved K⁺ storage performance. Part of Mg²⁺ and Ni²⁺ occupies the K⁺ layer, playing the role of a "nailed pillar", which restrains metal oxide layer gliding during the K⁺ (de)intercalation. The "Mg-Ni pinning effect" not only suppresses the phase transitions but also reduces the cell volume variation, leading to the improved cycle performance. Moreover, K_1/2Mn_5/6Mg_1/12Ni_1/12O₂ has low activation barrier energy for K⁺ diffusion and high electron conductivity as demonstrated by first-principles calculations, resulting in better rate capability. In addition, K_1/2Mn_5/6Mg_1/12Ni_1/12O₂ also delivers a higher reversible capacity owing to the participation of the Ni element in electrochemical reactions and the pseudocapacitive contribution. This study provides a basic understanding of structural evolution in layered Mn-based oxides and broadens the strategic design of cathode materials for PIBs.