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High-rate performance and super long-cycle stability of Na3V2(PO4)3 cathode material coated by diatomic doped carbon

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Abstract

Na3V2(PO4)3 is considered as one of the most promising cathodes for sodium ion batteries due to its excellent thermal stability, long cycle life and high energy density. However, the inferior intrinsic electronic conductivity which brings about the poor rate capability and cycling performance hinders its commercial application. Herein, the S–N co-doped carbon-coated Na3V2(PO4)3 (NVP@SNC) has been synthesized to resolve the problem. The prepared NVP@SNC forms a hierarchical structure assembled with nanosheets, which is in favor of the electrolyte infiltration and shortening the Na+ transmission distance. Numerous lattice defects can be induced in carbon layer by the co-doped elements (S–N), which reduce the Na+ diffusion energy barriers and provide adequate Na+ migration channels, thus jointly boosting the Na+ diffusion coefficient. Consequently, the NVP@SNC cathode shows a high reversible capacity with outstanding rate performance and super long-cycle stability. When discharged at 2.0C, it delivers the capacity near to the theoretical value with a capacity retention of 88.7% after 400 cycles. Even if the current is as high as 50.0C, a high capacity of 58.6 mAh·g−1 has been released, and 41.4 mAh·g−1 has been remained after the super long cycling of 4000 circles. This study is expected to supply a new thought of developing high-performance cathodes by diatomic doping for sodium ion battery.

Graphical abstract

摘要

Na3V2(PO4)3 由于其优异的热稳定性、长循环寿命和高能量密度，被认为在钠离子电池正极材料应用方面具有良 好的发展前景。然而，其电子导电率较低，导致电极倍率性能和循环性能较差，阻碍了商业化应用。针对该问题， 本文制备了由纳米片组装而成的硫-氮共掺杂碳包覆的Na3V2(PO4)3 (缩写为NVP@SNC)，该材料不仅具有良好 的电子导电性，而且孔隙丰富，有利于电解质的浸润并缩短Na+传输距离。此外，硫-氮共掺杂可在碳层中诱导产 生晶格缺陷，从而降低Na+扩散能垒，并增加Na+迁移通道，从而提高Na+扩散系数。因此，NVP@SNC 作为钠 离子电池正极材料不仅具有很高的可逆容量，并且展现了优异的倍率性能和超长的循环稳定性。在2.0C 倍率放 电时，其放电容量接近理论值，400 圈循环后容量保持为88.7%。即使在电流高达50.0C 时，初始放电容量也有 58.6 mAh·g‒1，经过4000 圈的超长循环后仍保留有41.4 mAh·g‒1，容量保持率为70.6%。由此可见，本文研究 的双原子掺杂碳包覆方案为开发高性能钠离子电池正极材料提供了新的思路。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 11964010, 11464014, 51862008, 52064014 and 52064013), the Natural Science Foundation of Hunan Province (No. 2020JJ4495) and the Youth Program of Hunan Provincial Education Department (No. 21B0522).

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  1. School of Physics and Electromechanical Engineering, Jishou University, Jishou, 416000, China

    Jia Kang, Ling Zhu, Fei-Yang Teng, Si-Qi Wang, Yong-Gang Huang, Yan-Hong Xiang & Zhe Chen

  2. School of Chemistry and Chemical Engineering, Jishou University, Jishou, 416000, China

    Xian-Wen Wu

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Kang, J., Zhu, L., Teng, FY. et al. High-rate performance and super long-cycle stability of Na3V2(PO4)3 cathode material coated by diatomic doped carbon. Rare Met. 42, 1570–1582 (2023). https://doi.org/10.1007/s12598-022-02204-w

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