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研究论文

钴掺杂提升夏威夷果壳基硬碳的储钠稳定性和高倍率容量

赵紫璞a, 孙雨涵a, 张静洁b, 郭文迪a, 鲍晓冰a, 罗巧梅a, 苟蕾a, 樊小勇a,*   

  1. a长安大学 材料科学与工程学院 西安 710061;
    b陕西交控绿色发展集团有限公司 西安 710100
  • 投稿日期:2026-01-11
  • 通讯作者: *E-mail: xyfan@chd.edu.cn (樊小勇); Tel.: 029-82337340; Fax: fax number: 029-82337340
  • 基金资助:
    西藏自治区重点研发项目(XZ202401ZY0104),陕西省国资委项目(ZXZJ-2024-018)

Cobalt-Doping Enhancing the Cyclability and High-rate Capacity of Macadamia Nut Shell-Based Hard Carbon

Zhao Zipua, Sun Yuhana, Zhang Jingjieb, Guo wendia, Bao Xiaobinga, Luo Qiaomeia, Gou Leia, Fan Xiaoyonga,*   

  1. aSchool of Material Science and Engineering, Chang'an University, Xi'an 710061, China;
    bCompany of Shaanxi Communications Holding Green Development Group, Xi'an 710100, China
  • Received:2026-01-11

生物质硬碳凭借原料来源丰富、成本低和环境友好等优点,已成为钠离子电池负极的研究热点。然而,其层间距小,导致钠离子嵌入/脱出困难、结构坍塌,最终造成其循环稳定性差及高倍率容量低,限制其商业化应用。本研究以夏威夷果壳为前驱体,通过调节掺杂钴离子浓度与合成工艺,制备了钴掺杂硬碳负极材料(Co-HC)。钴掺杂不仅增大层间距,促进石墨化,提升离子扩散动力学和电子导电性;还能将孔隙结构从微孔主导转变为介孔主导,大幅降低比表面积,促进Na+快速扩散,显著提升材料的倍率性能;并且Co-HC中相互连接的膨胀石墨结构可加速电子传输,石墨层周围的无定形碳以及含氧缺陷也为离子吸附提供了丰富的活性位点。电化学测试表明,Co-HC电极在30 mA g-1的电流密度下持续循环120圈仍显示322.4 mAh g-1的高稳定容量,即使在300 mA g-1大电流下循环900圈仍维持251.1 mAh g-1。倍率性能显示,即使提升到2000 mA g-1的超大电流,容量也能达到224.46 mAh g-1,容量保持率仍可达65.8%;当电流密度恢复到20 mA g-1时,Co-HC电极的容量可恢复到320.2 mAh g-1,充分证明了其卓越的循环寿命和高倍率容量。

关键词: 钠离子电池, 负极材料, 生物质硬碳, 钴掺杂, 结构调控

Biomass-derived hard carbon, with its advantages of abundant raw material sources, low cost, and environmental friendliness, has become the research hotspot of anodes for sodium-ion batteries. However, the inherent drawbacks of conventional biomass hard derived carbon, such as narrow interlayer spacing, sluggish Na+ diffusion kinetics, excessive specific surface area, and unsatisfactory structural stability, severely restrict its reversible capacity, cycle life, and high-rate capability, hindering its large-scale commercialization. In this study, macadamia nutshell was used as the biomass precursor to prepare cobalt-doped hard carbon anode materials (Co-HC), Systematic characterizations including transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, N2 adsorption-desorption measurement, and X-ray photoelectron spectroscopy (XPS) verify that the cobalt doping effectively enlarges the interlayer spacing from 0.371 nm to 0.389 nm, and significantly reduces the specific surface area from 182.805 m2 g-1 to 6.984 m2 g-1 by adjusting the doping concentration and synthesizing process. Cobalt doping not only increases the interlayer spacing, promoting graphitization, enhancing ion diffusion kinetics and electronic conductivity; it also promotes the pore structure transforms from micropore-dominated to mesopore-dominated, substantially reducing the specific surface area. This facilitates rapid Na⁺ diffusion and markedly improves the material's rate performance. Moreover, the expanded graphitic structure of Co-HC effectively enhances the electron conductivity, and the amorphous carbon surrounding the graphitic layers and the oxygen-containing defects provide abundant active sites for Na+ adsorption. Electrochemical testing indicates the Co-HC electrode shows a relatively stable capacity of 322.4 mAh g-1 after 120 cycles at a current density of 30 mA g-1. Even under a high current density of 300 mA g-1, it maintains a reversible capacity of 251.1 mAh g-1 after 900 cycles. The rate performance demonstrates that even at an exceptionally high current of 2000 mA g-1, the capacity reaches 224.46 mAh g-1 with a capacity retention of 65.8%. When the current density is reduced to 20 mA g-1, the Co-HC electrode recovers its capacity to 320.2 mAh g-1, fully demonstrating its outstanding cycle lifespan and high-rate performance.

Key words: Sodium -ion battery, Anode, Biomass-derived hard carbon, Cobalt-doping, Structural modification