Cationic ordering transition in oxygen-redox layered oxide cathodes

Abstract

Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox (OR) layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes. Here, we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_0.6Li_0.2Mn_0.8O₂ via in situ structural analysis. Comparing two different voltage windows, the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition. We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn⁴⁺ to Jahn-Teller Mn³⁺ and the concomitant NaO₆ stacking transformation from triangular prisms to octahedra, resulting in the loss of ribbon ordering and electrochemical decay. First-principles calculations reveal that Mn⁴⁺/Mn³⁺ charge ordering and alignment of the degenerate e_g orbital induce lattice-level collective Jahn-Teller distortion, which favors intralayer Mn-ion migration and thereby accelerates OR degradation. These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.

Keywords

cationic ordering / layered oxide cathodes / oxygen redox / sodium-ion batteries

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