<br>通过 NASICON Na4MnCr(PO4)3 阴极中的阴离子掺杂提高钠离子电池性能,Journal of Colloid and Interface Science

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通过 NASICON Na4MnCr(PO4)3 阴极中的阴离子掺杂提高钠离子电池性能
Journal of Colloid and Interface Science ( IF 9.4 ) Pub Date : 2024-02-22 , DOI: 10.1016/j.jcis.2024.02.150
Qing Zhu ₁ , Jinxin Wu ₁ , Wenhao Li ₁ , Xiuli Hu ₁ , Ningchen Tian ₂ , Liqing He ₃ , Yanwei Li ₁

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Na超离子导体NASICON）结构的NaMnCr（PO）（NMCP）拥有独特的三电子转移过程，为钠离子电池（SIB）提供了令人惊叹的能量密度。然而，目前其钠扩散动力学缓慢、本征电导率不足和结构稳定性不理想等问题阻碍了其实际应用。在此，开发了NMCP体系中Cl阴离子选择性取代PO基团中的O元素，以显着增强其电化学性能。结果证实，Cl掺杂样品的性能增强可归因于Cl掺杂后晶胞尺寸的增大、Na空位的产生以及Na2O键的减弱。相比之下，所制备的Na□MnCr(POCl)/C (NMCPC − 15/C)正极具有高容量（50 mA g-1 下为128.0 mAh/g）和优异的倍率性能（1000 mA g-1 下为73.0 mAh/g） NMCP/C 在 50 mA g-1 时仅提供 105.2 mAh/g，在 1000 mA g-1 时降至 47.4 mAh/g。同时，NMCPC - 15/C 在 500 次循环后在 1000 mA g-1 下的容量保持率为 60.7%，而 NMCP/C 在相同测试条件下仅为 37.1%。此外，NMCPC−15/C||硬碳（HC）全电池良好的性能和能量密度证实了NMCPC−15的潜在实用性。因此，氯离子掺杂到NMCP中在制备高性能材料方面具有实际应用前景。阴极材料和我们的工作还为应用阴离子掺杂策略来提高其他 NASICON 结构的 SIB 阴极的性能提供了新的灵感。

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Boosting sodium-ion battery performance by anion doping in NASICON Na4MnCr(PO4)3 cathode

Na superionic conductor NASICON)-structured NaMnCr(PO) (NMCP) possessing unique three-electron transfer process renders admirable energy density for sodium ion batteries (SIBs). However, the current issues like its sluggish Na diffusion kinetics, deficient intrinsic conductivity, and unsatisfactory structural stability, hinder its practical application. Herein, a selective replacement of O elements in PO group by Cl anions in the NMCP system was developed to significantly enhance its electrochemical performance. The results affirm that the enhanced performance of Cl doped samples can be attributed to the enlargement of cell size, the creation of Na vacancies and the weakness of Na2O bond after Cl doping. The as-prepared Na□MnCr(POCl)/C (NMCPC − 15/C) cathode delivers a high capacity (128.0 mAh/g at 50 mA g) and excellent rate performance (73.0 mAh/g at 1000 mA g) in contrast to NMCP/C that merely provides 105.2 mAh/g at 50 mA g and reduces to 47.4 mAh/g at 1000 mA g. Meanwhile, NMCPC − 15/C shows a capacity retention of 60.7 % at 1000 mA g after 500 cycles, while only 37.1 % for NMCP/C in the same test conditions. Moreover, the satisfactory performance and energy density of NMCPC − 15/C||hard carbon (HC) full cell confirm the potential practicality of NMCPC − 15. Therefore, chloride ions doping into NMCP has practical application prospects in the preparation of high-performance cathode materials and our work also offers new inspiration to apply anion doping strategies in promoting the performance of the other NASICON-structured cathodes for SIBs.

更新日期：2024-02-22

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