Mitigating Internal Gliding of a High-Voltage O3-Type Cathode via Na-Site Doping with High Ionic Potential Cations.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 42113644.
- Also identified by DOI 10.1021/acs.nanolett.6c01195.
- No licence information is recorded for this record.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
High-voltage O3-type cathodes promise higher energy densities for sodium-ion batteries but suffer from severe lattice strain, interlayer gliding, and structural degradation during cycling. Here, we report that Te<sup>4+</sup> doping into the Na 3a sites of NaNi<sub>0.35</sub>Fe<sub>0.2</sub>Mn<sub>0.3</sub>Cu<sub>0.05</sub>Ti<sub>0.1</sub>O<sub>2</sub> markedly improves its high-voltage cycling stability. Te<sup>4+</sup> doping suppresses stress accumulation, interlayer gliding, and intragranular cracking, thereby enhancing structural reversibility and electrochemical performance. Extending this strategy, Ca<sup>2+</sup>, Y<sup>3+</sup>, and Sm<sup>3+</sup> with similarly high ionic potentials preferentially occupy Na 3a sites, all exhibiting reduced lattice degradation and improved durability, confirming a universal "pinning effect". Notably, Ca<sup>2+</sup> doping enables kilogram-scale production, and the assembled 18650 cylindrical cell retains 89.9% capacity after 500 cycles. Mechanistically, strong ion-oxygen interactions stiffen the Na layer lattice, stabilizing the framework during Na (de)intercalation and suppressing (003) gliding. This work establishes high ionic potential Na-site doping as a broadly applicable design principle for durable high-voltage O3 cathodes.