Zhang Gaoyuan, Yin XingXing, Ning De, Chai Yan, Du Ruijie, Hao Dingbang, Wang Chunling, Liu Xueling, Gao Rui, Wang Jun, Yao Xiangdong, Li Yongli, Zhou Dong
Institute for Clean Energy Technology, North China Electric Power University, 102206, Beijing, P. R. China.
School of Materials, Sun Yat-Sen University, 518107, Shenzhen, P R. China.
Angew Chem Int Ed Engl. 2025 Jan 15;64(3):e202415450. doi: 10.1002/anie.202415450. Epub 2024 Dec 4.
Mn-based layered oxide cathodes for sodium-ion batteries with anionic redox reactions hold great potential for energy storage applications due to their ultra-high capacity and cost effectiveness. However, achieving high capacity requires overcoming challenges such as oxygen-redox failure, sluggish kinetics, and structural degradation. Herein, we employ an innovative crystal modulation strategy, using Mn-based NaLiMnO as a representative cathode material, which shows that the highly exposed {010} active facets enable an enhanced rate capability (119.6 mAh g at 10 C) with fast kinetics. Meanwhile, the reinforced Mn-O bond inhibits excessive oxidation of lattice oxygen and O-O cohesion loss, stabilizing and maintaining a long-enduring reversible oxygen-redox activity (100 % high capacity retention after 100 cycles at 0.5 C and 84.28 % retention after 300 cycles at 5 C). Time-resolved operando two-dimensional X-ray diffraction reveals the robust structural stability, zero-strain behavior, and suppressed phase transition with ultra-low volume variation during cycling at different rates (0.1 C: 1.75 %, 1 C: 0.31 %, 5 C: 0.04 %). Additionally, the full cell coupled with hard carbon achieves a high energy density of approximately 211 Wh kg with superior performance. This work highlights the significance of crystal modulation and presents a universal approach in developing Mn-based oxide cathodes with stable anionic redox for high-performance sodium-ion batteries.
具有阴离子氧化还原反应的钠离子电池锰基层状氧化物阴极，因其超高容量和成本效益在储能应用中具有巨大潜力。然而，要实现高容量需要克服诸如氧氧化还原失效、动力学迟缓以及结构降解等挑战。在此，我们采用一种创新的晶体调制策略，以锰基NaLiMnO作为代表性阴极材料，结果表明高度暴露的{010}活性面能够实现增强的倍率性能（10C时为119.6 mAh g）以及快速的动力学。同时，强化的Mn - O键抑制了晶格氧的过度氧化和O - O内聚损失，稳定并维持了持久的可逆氧氧化还原活性（0.5C下100次循环后容量保持率为100%，5C下300次循环后保持率为84.28%）。时间分辨原位二维X射线衍射揭示了在不同倍率（0.1C：1.75%，1C：0.31%，5C：0.04%）循环过程中具有稳健的结构稳定性、零应变行为以及抑制的相变和超低的体积变化。此外，与硬碳耦合的全电池实现了约211 Wh kg的高能量密度以及优异的性能。这项工作突出了晶体调制的重要性，并提出了一种开发具有稳定阴离子氧化还原的高性能钠离子电池锰基氧化物阴极的通用方法。
