目的 通过微弧氧化技术与碳纳米管复合改性制备锂离子电池负极材料,并系统研究它对电池电化学性能的调控机制。方法 采用微弧氧化技术原位制备锐钛矿相二氧化钛多孔膜层,将碳纳米管复合于二氧化钛表面,形成复合电极。通过扫描电镜、X射线衍射和拉曼光谱对材料的微观形貌和晶体结构进行表征,进一步结合恒流充放电循环、循环伏安及电化学阻抗谱测试,系统分析电极材料的储能性能、氧化还原反应特性及界面电荷传输动力学。结果 扫描电镜结果显示,通过微弧氧化制备的TiO2膜层呈多孔结构,孔径为2~50 μm,在复合碳纳米管后,其表面形成了纳米纤维交织的导电网络。电化学测试结果表明,复合电极在电流密度100 mA/g下,第2圈的比容量达到339.26 mA·h/g,在150次循环后其容量保持率为74.3%,显著优于未复合的负极（其容量保持率为45.2%）。倍率性能测试结果显示,在10 C倍率下复合负极仍保持着251.92 mA·h/g的比容量,是0.5 C时初始容量的74.3%。结论 碳纳米管与二氧化钛多孔骨架的协同作用有利于提升电极的电子导电性,抑制体积的膨胀,并通过多级孔道优化了Li+传输动力学。该研究为负极-集流体一体化电极的设计提供了新思路,未来需进一步优化碳纳米管分布均匀性,以提升长期循环稳定性。
Abstract
This study aims to enhance the electrochemical performance of lithium-ion battery anodes by integrating carbon nanotubes with a titanium dioxide porous framework fabricated via micro-arc oxidation. A porous anatase-phase carbon nanotubes layer is in situ synthesized on a titanium substrate using micro-arc oxidation under optimized parameters (current density: 17 A/dm2, frequency: 500 Hz, duty cycle: 45%, processing time: 2 min), followed by uniform carbon nanotubes dispersion onto the carbon nanotubes surface via the blade-coating method. Structural and morphological characterization of the composite electrode (CNTs/MAO-Ti) is performed via Scanning Electron Microscopy (SEM), X-ray diffraction, and Raman spectroscopy. Scanning electron microscopy analysis reveals a hierarchical porous architecture in the MAO-Ti layer with pore sizes ranging from 2 to 50 μm, while carbon nanotubes form an interwoven conductive network on the carbon nanotubes surface, enhancing surface roughness and electronic conductivity. X-ray diffraction patterns confirm the anatase-phase crystallinity of titanium dioxide (PDF#84-1285), with characteristic peaks at 25.3° (101), 37.8° (004), and 48.0° (200), and Raman spectroscopy identifies distinct vibrational modes at 146 cm-1 (Eg), 394 cm-1 (B1g), and 640 cm-1 (Eg), which is consistent with anatase structure. The Raman D/G band intensity ratio indicates that reduced defect density and improved graphitic ordering in the carbon nanotubes composite are attributed to interfacial coupling with titanium dioxide. Electrochemical performance is evaluated through methods including galvanostatic charge-discharge cycling, cyclic voltammetry, and electrochemical impedance spectroscopy. At 100 mA/g, the CNTs/MAO-Ti composite delivers a second-cycle specific capacity of 339.26 mA·h/g, significantly outperforming the pure MAO-Ti electrode (125 mA·h/g), and retains 74.3% of its initial capacity after 150 cycles, compared with 45.2% for the unmodified titanium dioxide. Rate capability tests demonstrate a capacity retention of 74.3% at 10 C (251.92 mA·h/g) relative to 0.5 C, while cyclic voltammetry curves at scan rates of 0.1-2 mV/s reveal pseudocapacitive contributions and high reversibility of Li+ intercalation/deintercalation. EIS analysis reveals a notable decrease in charge-transfer resistance relative to MAO-Ti, demonstrating optimized charge transport kinetics of the composite. Li+ diffusion coefficients, calculated from Warburg impedance slopes, are 6.03×10-15 m2/s for MAO-Ti and 2.21×10-17 m2/s for CNTs/MAO-Ti, indicating that the hierarchical pore structure of titanium dioxide and carbon nanotubes' conductive network synergistically offset limitations in solid-state Li+ diffusion. The initial Coulombic efficiency (47.4%) is attributed to irreversible SEI formation and lithium loss, but it is stabilized near 100% after subsequent cycles, reflecting improved interfacial stability. The enhanced performance is attributed to three key mechanisms: (1) The titanium dioxide porous skeleton provides rapid Li+ transport channels; (2) The carbon nanotubes network reduces electronic resistance and suppresses volume expansion via mechanical interlocking; and (3) Interfacial coupling between carbon nanotubes and titanium dioxide optimizes charge transfer kinetics. This work validates the effectiveness of micro-arc oxidation combined with carbon nanotubes modification for designing integrated anode-current collector systems, where the "porous framework-conductive network- interface coupling" architecture enhances both structural stability and electrochemical activity. However, long-term cycling stability remains limited by uneven carbon nanotubes distribution and SEI dynamic reconstruction. Future studies should focus on optimizing carbon nanotubes dispersion uniformity and engineering interfacial phases to further improve Li+ solid-state diffusion and cyclability. The proposed strategy is applicable to other metal oxide systems, offering a scalable pathway for high-performance lithium-ion battery anodes.
关键词
微弧氧化 /
锂离子电池负极 /
碳纳米管 /
二氧化钛 /
电化学性能
Key words
micro-arc oxidation /
lithium-ion battery anode /
carbon nanotubes /
titanium dioxide /
electrochemical performance
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基金
国家自然科学基金（51672120）; 黑龙江省自然科学基金（LH2023E101）; 黑龙江省教学改革项目（SJGYB2024687）
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