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电化学储能中的钠离子电池，因资源丰度及成本优势，是大规模储能系统极具产业化潜力的技术之一。其正极材料的聚阴离子型材料因稳定结构和诱导效应展现出优异的循环稳定性和电压平台特性，其中Na_3V2(PO4)3(NVP)正极材料被广泛研究。本文构筑了钛(Ti)梯度取代与双相碳包覆(原位无定形碳和碳纳米管网络)协同优化的NASICON型Na3-xV2-xTix(PO4)3@C(0≤x≤1)正极材料，系统揭示了Ti取代对晶体结构演化与电化学性能的协同调控机制。Rietveld精修结合能量色散光谱法(EDS)证实，Ti成功进入晶格并诱导晶格参数收缩，从而有效拓宽钠离子传输通道。通过液相包覆法构建的原位无定形碳与高度石墨化的碳纳米管复合构建三维导电网络，显著提升电子电导率。经筛选得到最佳Ti取代比例和最优碳包覆涂层制备方法，电化学测试表明NVP-Ti02@C在01 C下放电比容量达11501 mAh/g,10 C高倍率下放电比容量达9098 mAh/g,1 C倍率下循环320周后容量保持率为95%。该方法为聚阴离子型钠电正极材料的体相-界面协同优化提供了新策略。
Abstract：In electrochemical energy storage,sodium-ion batteries(SIBs),with abundant resources and cost advantages,are a large-scale energy storage technology with great industrialization potential.Among cathode materials,polyanionic materials show excellent cycling stability and voltage plateau characteristics due to their stable structures and inductive effects.This study designed and fabricated a NASICON-type Na3-xV2-xTix(PO4)3@C(0≤x≤1) cathode material with Ti gradient substitution and dual-phase carbon coating for synergistic optimization.Rietveld refinement and EDS confirmed uniform Ti distribution in the lattice,inducing lattice contraction to expand sodium-ion diffusion channels.A 3D conductive network of in-situ amorphous carbon and carbon nanotubes was built via liquid-phase coating,enhancing electronic conductivity.The optimal Ti substitution and carboncoating method were identified.Electrochemical tests showed NVP-Ti0.2@C delivered 115.01 mAh/g at 0.1 C,90.98 mAh/g at 10 C,and 95% capacity retention after 320 cycles at 1 C,offering a new strategy for synergistic ally optimizing the bulk and interfacial properties of poly anionic cathodes for SIBs.
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基本信息:
DOI：10.19996/j.cnki.ChinBatlnd.2025.06.002
中图分类号:TM912;TQ131.12
引用信息:
[1]韩影,裴柳,王义飞,等.聚阴离子型钠离子电池正极材料钛梯度取代协同碳包覆研究[J].电池工业,2025,29(06):455-462.DOI:10.19996/j.cnki.ChinBatlnd.2025.06.002.
基金信息:
国家自然基金项目（22279007）