Na3Zr2Si2PO12NaNi0.33Cu0.06Fe0.28Mn0.330.9Ti0.1O2复合制备高性能钠离子O3型层状氧化物正极材料

Preparation of high-performance sodium-ion O3-type layered oxide cathode materials by Na3Zr2Si2PO12 composite with Na(Ni0.33Cu0.06Fe0.28Mn0.330.9Ti0.1O2

  • 摘要: O3型层状氧化物具有高能量密度、高工作电压等优点,但随着循环进行,其复杂的相变致使空间结构收缩、体积变化大,阻碍Na+的传输,容易产生容量缩减、界面阻抗增大等一系列现象。本文通过钠超离子导体Na3Zr2Si2PO12与O3型层状氧化物Na(Ni0.33Cu0.06Fe0.28Mn0.330.9Ti0.1O2的复合,提高了正极材料的离子扩散系数和离子电导率,降低了界面阻抗;在高电压和长循环的过程中,Na3Zr2Si2PO12起到了一定的补钠作用。复合正极材料Na(Ni0.33Cu0.06Fe0.28Mn0.330.9Ti0.1O2-5% Na3Zr2Si2PO12在0.5 C和1 C下分别有123.0 mAh/g和110.6 mAh/g的放电比容量,循环100圈后容量保持率分别高达68.9%和65.8%。

     

    Abstract: O3-type layered oxides exhibit remarkable advantages in terms of high energy density and high operating voltage. However, as cycling progresses, their intricate phase transitions lead to contraction of the spatial structure and substantial volume changes. These changes impede the diffusion of Na⁺ and are likely to trigger a series of issues, including capacity fading and an increased interfacial impedance. In this study, compounding sodium superionic conductors with O3-type layered oxides to fabricate composite cathode materials is proposed as an effective optimization strategy. Accordingly, the sodium superionic conductor Na3Zr2Si2PO12 and the O3-type layered oxide Na(Ni0.33Cu0.06Fe0.28Mn0.33)0.9Ti0.1O2 were synthesized and subsequently composited to fabricate a series of cathode materials. Na3Zr2Si2PO12 was used to enhance ionic conductivity, reduce interfacial impedance, and replenish highly desodiated Na+. The composite cathode Na(Ni0.33Cu0.06Fe0.28Mn0.33)0.9Ti0.1O2-5% Na3Zr2Si2PO12 exhibited outstanding electrochemical performance. It delivered discharge-specific capacities of 123.0 mAh/g and 110.6 mAh/g at 0.5 C and 1 C, respectively, with capacity retentions of 68.9% and 65.8% after 100 cycles.

     

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