用于钠离子电池的高倍率、耐用阴极：掺锑 O3 型镍/锰基层状氧化物,ACS Nano

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用于钠离子电池的高倍率、耐用阴极：掺锑 O3 型镍/锰基层状氧化物
ACS Nano ( IF 15.8 ) Pub Date : 2022-10-19 , DOI: 10.1021/acsnano.2c04702
Tao Yuan, Siqing Li, Yuanyuan Sun, Jeng-Han Wang, An-Jie Chen, Qinfeng Zheng, Yixiao Zhang, Liwei Chen, Gyutae Nam, Haiying Che, Junhe Yang, Shiyou Zheng, Zi-Feng Ma, Meilin Liu

O3 型层状氧化物由于其高理论容量而被广泛研究作为钠离子电池 (SIB) 的阴极。然而，它们的倍率性能和耐久性受到曲折的 Na ⁺扩散通道和 Na + 脱嵌过程中复杂的相演化^的限制。在这里，我们报告了我们的发现，揭示了通过替代 Sb 掺杂显着提高 O3-NaNi _0.5 Mn _{0.5– x} Sb _x O ₂ (NaNMS) 的稳定性和倍率能力的机制，这可以改变过渡的配位环境和化学键结构中的金属 (TM) 离子，导致具有更宽 Na ^{+的更稳定的结构}运输渠道。此外，NaNMS 纳米粒子是通过晶粒生长过程中的表面能调节获得的。Sb 掺杂和纳米结构的协同效应大大降低了离子迁移能垒，同时增加了重复 Na ⁺提取/插入过程中结构演化的可逆性。优化的 NaNMS-1 电极在 0.2 C时的可逆容量为 212.3 mAh g ^{–1 ，在 50 C 时的可逆容量为 74.5 mAh g}^–1，在 -20 °C 的低温下循环 100 次后容量损失最小。这种电化学性能优于大多数已报道的可充电 SIB 中使用的层状氧化物正极。

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A High-Rate, Durable Cathode for Sodium-Ion Batteries: Sb-Doped O3-Type Ni/Mn-Based Layered Oxides

O3-Type layered oxides are widely studied as cathodes for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, their rate capability and durability are limited by tortuous Na⁺ diffusion channels and complicated phase evolution during Na⁺ extraction/insertion. Here we report our findings in unravelling the mechanism for dramatically enhancing the stability and rate capability of O3-NaNi_0.5Mn_0.5–xSb_xO₂ (NaNMS) by substitutional Sb doping, which can alter the coordination environment and chemical bonds of the transition metal (TM) ions in the structure, resulting in a more stable structure with wider Na⁺ transport channels. Furthermore, NaNMS nanoparticles are obtained by surface energy regulation during grain growth. The synergistic effect of Sb doping and nanostructuring greatly reduces the ionic migration energy barrier while increasing the reversibility of the structural evolution during repeated Na⁺ extraction/insertion. An optimized NaNMS-1 electrode delivers a reversible capacity of 212.3 mAh g^–1 at 0.2 C and 74.5 mAh g^–1 at 50 C with minimal capacity loss after 100 cycles at a low temperature of −20 °C. Such electrochemical performance is superior to most of the reported layered oxide cathodes used in rechargeable SIBs.

更新日期：2022-10-19

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