当前日益增长的能源需求与不可再生化石能源枯竭的矛盾日益加剧，而新能源能平稳利用则亟需大量的储能器件。锂离子电池由于较高能量密度而广泛用于解决新能源转换和储存问题。本文针对高性能锂离子电池负极材料进行开发研究。由于过渡金属硫化物具有比石墨高得多的理论比容量，近年来受到广大科研者的极大关注。其中，双金属硫化物与单一金属硫化物相比，可以生成更多的氧化还原位活性位点，但存在导电性与结构稳定性差的问题而制约了其发展。构建过渡金属硫化物与碳纳米管(CNTs)的包覆结构，可协同发挥两者的效应，以获得综合电化学性能优良的复合电极材料。本文通过水热法合成了两种不同的CNTs/双金属硫化物复合材料，以期制备出具有高比电容、高倍率性能、长循环寿命的锂离子电池负极材料，探究了所得材料结构与储锂性能之间的构效关系及调控机制。主要工作如下：

 (1) 以CNTs为骨架，通过多巴胺的原位聚合制备了CNTs@PDA（聚多巴胺），然后通过水热法在其上原位沉积CoMoS₄而获得了比表面积为148.9 m²/g、CoMoS₄含量占比为64.23%的CNTs@PDA/CoMoS₄复合材料。以CNTs@PDA/CoMoS₄作为锂离子电池负极材料，在0.1 A/g时循环100圈后其放电比容量仍能保持在1025.2 mAh/g，并且在1 A/g下进行200次充放电循环后仍具有490.3 mAh/g的可逆容量。此外，储锂性能研究表明CNTs@PDA/CoMoS₄电极的电容贡献为57.8%以上。良好的电化学性能得益于PDA通过羟基增强了CoMoS₄纳米颗粒在CNTs上的的紧密沉积，而CNTs有效地降低了具有高活性位点的CoMoS₄纳米粒子团聚问题，实现了CoMoS₄纳米颗粒均匀地生长在CNTs@PDA表面。此外，CNTs的高导电性可以促进Li⁺的扩散，有效提高离子传输效率，且CNTs的骨架稳定性有效缓解了复合材料的体积膨胀效应。

 (2) 以CNTs为碳基底材料，先构筑出CNTs@PDA，然后通过水热反应将FeCo₂S₄纳米粒子附着沉积在其上，最后通过碳化处理制备出了比表面积为75.3 m²/g、FeCo₂S₄含量占比为55.5%的CNTs@NC/FeCo₂S₄复合材料。所获得的复合材料充放电循环稳定性以及倍率性能得到明显的提升，在电流密度为0.1 A/g下进行80次充放电循环，CNTs@NC/FeCo₂S₄活性电极仍然具有884.6 mAh/g的放电比容量。且在大的电流密度2 A/g下进行300次循环后，复合材料电极仍能提供481.6 mAh/g的比容量。储锂动力学研究表明CNTs@NC/FeCo₂S₄储能主要由电容过程贡献。CNTs@NC/FeCo₂S₄电极表现出良好的储能容量、循环稳定性和倍率性能，归因于PDA起着促进双金属硫化物FeCo₂S₄与CNTs之间紧密均匀包覆的桥梁作用；且将PDA进一步碳化成电导率更高的炭层，既大大降低了活性物质在锂离子嵌入与脱出过程中的体积变化问题，又提升了三元复合材料CNTs@NC/FeCo₂S₄的导电性能。

At present, the contradiction between the increasing energy demand and the exhaustion of non-renewable fossil energy is intensifying, and a large number of energy storage devices are urgently needed for the stable utilization of new energy. Lithium-ion batteries are widely used to solve new energy conversion and storage problems due to their higher energy density. In this paper, the development and research of high-performance lithium-ion battery anode materials are carried out. Transition metal sulfides have received great attention from researchers in recent years due to their much higher theoretical specific capacity than graphite. Among them, bimetallic sulfides can generate more redox active sites than single metal sulfides, but the problems of poor electrical conductivity and structural stability restrict their development. Constructing the coating structure of transition metal sulfides and carbon nanotubes (CNTs) can synergistically exert their effects to obtain composite electrode materials with excellent comprehensive electrochemical performance. In this paper, two different CNTs/bimetallic sulfide composites were synthesized by hydrothermal method to prepare lithium-ion battery anode materials with high specific capacitance, high rate performance and long cycle life.

(1) CNTs@PDA (polydopamine) was prepared by in-situ polymerization of dopamine with CNTs as skeleton, and then CoMoS₄ was in-situ deposited on it by hydrothermal method to obtain the CNTs@PDA/CoMoS₄ composite that specific surface area achieved 148.9 m²/g and the content of CoMoS₄ accounted for 64.2%. As the anode material for Li-ion batteries, the discharge specific capacity of CNTs@PDA/CoMoS₄ can still be maintained at 1025.2 mAh/g after 100 cycles at 0.1 A/g. And it still has a reversible capacity of 490.3 mAh/g after 200 charge-discharge cycles at 1 A/g. In addition, the lithium storage performance study shows that the capacitance contribution of CNTs@PDA/CoMoS₄ electrode is more than 57.8%. The good electrochemical performance is attributed to the enhanced compact deposition of CoMoS₄ nanoparticles on PDA through hydroxyl groups. In this encapsulated ternary material, CNTs effectively reduce the agglomeration problem of CoMoS₄ nanoparticles with high active sites, and realize the uniform growth of CoMoS₄ nanoparticles on the surface of CNTs@PDA. In addition, the high conductivity of CNTs can promote the diffusion of Li⁺ and effectively improve the ion transport efficiency, and the framework stability of CNTs can effectively alleviate the volume expansion effect of the composites.

 (2) CNTs@PDA was first constructed with CNTs as carbon base material, and then FeCo₂S₄ nanoparticles were attached and deposited on it through hydrothermal reaction. Finally, the CNTs@NC/FeCo₂S₄ composite that specific surface area of 75.3 m²/g and FeCo₂S₄ content of 55.5% were prepared by carbonization treatment. The charge-discharge cycle stability and rate performance of the obtained composites were significantly improved. The CNTs@NC/FeCo₂S₄ electrode still had a high rate of 884.6 mAh/g after 80 charge-discharge cycles at 0.1 A/g. And after 300 cycles at a high current density of 2 A/g, the composite electrode can still provide a specific capacity of 481.6 mAh/g. The studies of Li-storage kinetics show that the energy storage of CNTs@NC/FeCo₂S₄ is mainly contributed by capacitive processes. The reason for the good electrochemical performance of the CNTs@NC/FeCo₂S₄ electrode may be that PDA acts as a bridge to promote the tight and uniform coating between the FeCo₂S₄ and CNTs. The subsequent carbonization process further strengthens the stability of this coating structure, and further carbonizes the PDA into a carbon layer with higher conductivity, which not only greatly reduced the volume change of the active material during the intercalation and deintercalation of Li⁺, but also improved the electrical conductivity of the ternary composite CNTs@NC/FeCo₂S₄, and the cycle stability and rate performance of the composite were significantly improved.

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