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磷酸钒钠(Na3V2(PO4)3)具有较高的工作电压、快速的Na+扩散和良好的结构稳定性，是高性能钠离子电池的优选正极材料。然而，较低的本征电子导电性严重阻碍了它的实际应用。本研究设计并制备了Bi3+掺杂的Na3V2-xBix(PO4)3正极材料。Bi3+掺杂策略可以显著减小其带隙和Na+扩散能垒，因此显著改善了其电荷转移动力学和电化学性能。改性后的Na3V1.95Bi0.05(PO4)3@C正极材料在1C倍率下可逆比容量为117.77 mAh·g-1,20C下具有85.21 mAh·g-1的倍率容量；在5C下经过1300次充放电循环后，每循环的容量衰减率仅为0.006 9%。此外，通过原位X射线衍射阐释了Na3V1.95Bi0.05(PO4)3与NaV1.95Bi0.05(PO4)3之间存在高度可逆的双相转变。本研究为Na3V2(PO4)3正极在高性能钠离子电池中的实际应用提供了数据支持。
Abstract：Na3V2(PO4)3 has attracted significant attention as a viable cathode for high-performance sodium ion batteries owing to its satisfactory operating voltage, fast Na+ diffusion and thrilling structural stability.Nevertheless, its low intrinsic electronic conductivity severely impedes its practical applications.In this work, a Bi3+ doped Na3V2(PO4)3 is deliberately designed and prepared.The Bi3+-doped strategy not only significantly reduces its band gap, but also decreases Na+ diffusion energy barrier.Consequently, the dramatically boosted charge transfer kinetics and electrochemical performances are achieved.The modified Na3V1.95Bi0.05(PO4)3@C possesses a noteworthy rate capacity of 85.21 mAh·g-1 at 20C and an exceedingly low capacity attenuation of 0.006 9% per cycle at 5C after 1300 charging/discharging cycles.Moreover, a highly reversible bi-phase transition between Na3V1.95Bi0.05(PO4)3 and NaV1.95Bi0.05(PO4)3 is also interpreted based on the in-situ XRD.This research is beneficial to promote its large-scale applications of Na3V2(PO4)3 cathode for high-performance sodium ion batteries.
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基本信息:
DOI：10.20062/j.cnki.CN37-1453/N.2025.03.008
中图分类号:TQ131.12;TM912
引用信息:
[1]李纪阳,张延磊,张翔,等.Bi~(3+)掺杂磷酸钒钠的晶体结构调控与储钠性能研究[J].鲁东大学学报(自然科学版),2025,41(03):269-277.DOI:10.20062/j.cnki.CN37-1453/N.2025.03.008.
基金信息:
国家自然科学基金(22309072,52173075,21806070); 山东省自然科学基金(ZR2023QB176)