Electronic States Tailoring and Pinning Effect Boost High-Power Sodium-Ion Storage of Oriented Hollow P2-Type Cathode Materials

Fierce phase transformation and limited sodium ion diffusion dynamics are critical obstacles that hinder the practical energy storage applications of P2-type layered sodium transition metal oxides (Na_xTMO₂). Herein, a synergistic strategy of electronic state tailoring and pillar effect was carefully implemented by substituting divalent Mg²⁺ into Na_0.67Ni_0.33Mn_0.67O₂ material with unique oriented hollow rodlike structures. Mg²⁺substitution can not only facilitate the anionic oxygen redox reactions and electronic conductivity through increasing the electronic states at Femi energy but also act as pillars within TMO₂ layers to alleviate the severe phase transformation to improve structure stability. Moreover, the oriented hollow structure incorporating sufficient buffer spaces and rationally exposed electrochemically active facets effectively alleviates the stresses induced by low volume changes of 8% and provides more open channels for Na⁺ ion diffusion without crossing multiple grain boundaries. Hence, the Na_0.67Mg_0.08Ni_0.25Mn_0.67O₂ cathode showed a superior rate capability with high energy density and cycling stability for sodium-ion storage. The underlying mechanisms of these achievements were deciphered through diversified dynamic analysis and the first principle calculations, providing new insights into P2-type Na_xTMO₂ cathodes for the infinite prospect as an alternative to lithium-ion batteries.