无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ

无机盐工业 ›› 2025, Vol. 57 ›› Issue (5): 79-86.doi: 10.19964/j.issn.1006-4990.2024-0252

• 研究与开发 • 上一篇    下一篇

Mo-Mn双掺杂与碳纳米管复合协同提升Na4Fe3(PO42P2O7/C材料性能研究

陈彤彤1,2(), 韩现英1,2, 杰梦玲1,2, 李建刚1,2()   

  1. 1.北京石油化工学院新材料与化工学院,北京 102617
    2.燃料清洁化及高效;催化减排技术北京市重点实验室,北京 102617
  • 收稿日期:2024-05-07 出版日期:2025-05-10 发布日期:2024-06-18
  • 通讯作者: 李建刚(1966— ),男,博士,教授,研究方向为电化学能源转换与存储材料;E-mail:lijiangang@bipt.edu.cn
  • 作者简介:陈彤彤(1995— ),女,硕士研究生,研究方向为钠离子电池正极材料;E-mail:ctt10105204@163.com
  • 基金资助:
    北京市教育委员会科研计划项目(KM202310017003)

Synergistically enhanced properties of Na4Fe3(PO42P2O7/C material by Mo-Mn dual doping and carbon nanotube composite

CHEN Tongtong1,2(), HAN Xianying1,2, JIE Mengling1,2, LI Jiangang1,2()   

  1. 1. College of New Materials and Chemical Engineering,Beijing Institute of Petrochemical Technology,Beijing 102617,China
    2. Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology,Beijing 102617,China
  • Received:2024-05-07 Published:2025-05-10 Online:2024-06-18

摘要:

为提升钠离子电池正极材料Na4Fe3(PO42P2O7/C(NFPP)的导电性及高倍率充放电性能,采用喷雾干燥法制备了Mo-Mn双掺杂及复合碳纳米管(CNTs)改性的NFPP材料。通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、恒电流间歇滴定技术(GITT)及其他物理和电化学测试技术,系统分析了改性NFPP材料的结构与性能。研究结果表明,与单一Mo6+掺杂样品相比,Mo6+、Mn2+协同双掺杂能够进一步降低电荷传递阻抗,提高钠离子扩散系数,从而显著提升材料的电化学性能。所制备的Na4Fe2.87Mo0.1Mn0.03(PO42P2O7/C材料在0.1C、5.0C和10.0C倍率下的可逆容量分别达到122.6、100.3、95.6 mA·h/g。进一步复合质量分数为5%的碳纳米管后,材料的电荷传递阻抗降低至313 Ω,钠离子扩散系数提高至4.23×10-10 cm2/s,从而显著改善了材料的倍率性能和循环性能。改性后的材料在0.1C、5.0C和10.0C倍率下的可逆容量分别提升至123.0、109.5、104.4 mA·h/g,且在10.0C倍率下循环350次后容量保持率高达92.52%。该研究表明,Mo-Mn双掺杂结合碳纳米管复合改性是提升NFPP材料电化学性能的有效策略,为高性能钠离子电池正极材料的开发提供了重要的理论和实验依据。

关键词: 钠离子电池, Na4Fe3(PO42P2O7/C, Mo-Mn双掺杂, 碳纳米管

Abstract:

To improve the conductivity and high rate charge-discharge performance of Na4Fe3(PO42P2O7/C(NFPP) cathode material for sodium ion batteries,Mo-Mn dual doped and composite carbon nanotubes(CNTs) modified NFPP materials were prepared by spray drying.The structure and properties of modified NFPP materials were analyzed using X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),galvanostatic intermittent titration technique(GITT),and other physical and electrochemical testing techniques.The results indicated that compared to Mo6+-doped sample,the synergistic dual doping of Mo6+ and Mn2+ could further reduce the charge transfer impedance,improve the sodium ion diffusion coefficient,and enhance the electrochemical performance.The reversible capacities of Na4Fe2.87Mo0.1Mn0.03(PO42P2O7/C material at 0.1C,5.0C,and 10.0C rates were 122.6,100.3,and 95.6 mA·h/g,respectively.After further composite modification with 5% CNTs,the charge transfer impedance was further reduced to 313 Ω,and the sodium ion diffusion coefficient was increased to 4.23×10-10 cm2/s,further improving the rate performance and cycling performance.Its reversible capacities at 0.1C,5.0C,and 10.0C rates were increased to 123.0,109.5,and 104.4 mA·h/g,respectively,and the capacity retention after 350 cycles at 10.0C rates was as high as 92.52%.This study indicated that Mo-Mn dual doping and carbon nanotubes composite modification were effective strategies for improving the electrical performance of NFPP,providing important theoretical and experimental basis for the development of high⁃performance cathode materials for sodium ion batteries.

Key words: sodium ion batteries, Na4Fe3(PO42P2O7/C, Mo-Mn dual doping, carbon nanotubes

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