Sustainable Anionic Redox by Inhibiting Li Cross-Layer Migration in Na-Based Layered Oxide Cathodes.
basic_science · Level V
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- Record sourced from PubMed, PMID 38324715.
- Also identified by DOI 10.1021/acsnano.3c11146.
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Abstract
The irrational utilization of an anionic electron often accompanies structural degradation with an irreversible cation migration process upon cycling in sodium-layered oxide cathodes. Moreover, the insufficient understanding of the anionic redox involved cation migration makes the design strategies of high energy density electrodes even less effective. Herein, a P3-Na<sub>0.67</sub>Li<sub>0.2</sub>Fe<sub>0.2</sub>Mn<sub>0.6</sub>O<sub>2</sub> (P3-NLFM) cathode is proposed with the in-plane disordered Li distribution after an in-depth remolding of the Li ribbon-ordered P3-Na<sub>0.6</sub>Li<sub>0.2</sub>Mn<sub>0.8</sub>O<sub>2</sub> (P3-NLM) layered oxide. The disordered Li sublattice in the transition metal slab of P3-NLFM leads to the dispersed <b>|</b>O<sub>2p</sub> orbitals, the lowered charge transfer gap, and the suppressed phase transition at high voltages. Then the enhanced Mn-O interaction and electronic stability are disclosed by the crystal orbital Hamilton population (COHP) analysis at high voltage in P3-NLFM. Furthermore, <i>ab initio</i> molecular dynamics (AIMD) simulation suggests the order/disorder of the transition metal layer is highly correlated with the stability of the Li sublattice. The cross-layer migration and loss of Li in P3-NLM are suppressed in P3-NLFM to enable the high reversibility upon cycling. As a result, the P3-NLFM delivers a high capacity of 163 mAh g<sup>-1</sup> without oxygen release and an enhanced capacity retention of 81.9% (vs 42.9% in P3-NLM) after 200 cycles, which constitutes a promising approach for sustainable oxygen redox in rechargeable batteries.