基于沥青制备锂硫电池正极材料及其性能研究

锂硫电池具有理论能量密度高（~2600 Wh kg⁻¹）和成本低等优点，是最具潜力的下一代高能电池技术。但正极材料硫导电率差、多硫化物穿梭效应和缓慢的氧化还原反应动力学等问题，严重阻碍锂硫电池的实际应用。为了解决上述问题，本文基于沥青的强吸附、富含杂原子、大分子结构、粘度大和吸波性差等特性，设计并制备系列硫正极复合材料，同时深入研究硫正极复合材料对降低电池极化、吸附多硫化物和提升多硫化物转化动力学的作用机制。主要研究内容如下：

基于沥青富含杂原子和强吸附特性，以具有多层级结构的MnO二次颗粒为模板，沥青为碳源，制备出富含氮、氧、硫杂原子的多层级介孔碳微球（HMHC）。得益于HMHC具有孔容量大、电子导电性好、对锂多硫化物吸附能力强、电催化效果显著等特点，该HMHC作为硫宿主能有效抑制多硫化物穿梭，提升电化学反应动力学。以其作为硫载体材料的锂硫电池，在电解质/硫比为8 μL mg⁻¹和 0.2 C倍率下，表现出优异的电化学性能，初始放电比容量为1100.6 mAh g⁻¹，循环200次后容量保持率为91%。多层级介孔杂原子掺杂碳材料为解决锂硫电池多硫化物穿梭等问题，提供了一种简便的方法。

基于沥青富含杂原子和大分子结构特性，以沥青为碳源、尿素为软模板、环烷酸钴为钴源，制备“亲硫”的单原子钴以CoN₃S结构嵌入在“亲锂”的杂原子掺杂碳材料（SACo@HC）。密度泛函理论计算和实验结果表明，SACo@HC中CoN₃S配位结构的单原子钴，可以显著增强载体材料对多硫化物的吸附作用和氧化还原动力学，提升活性材料的利用率及倍率性能。因此，S-SACo@HC硫正极材料，0.05 C倍率下放电比容量为1425.1 mAh g⁻¹，4 C倍率下放电比容量高达745.9 mAh g⁻¹。该工作加深了对多硫化锂吸附和界面工程的理解，并为解决锂硫电池长期存在的多硫化物穿梭问题提供思路。

基于沥青吸波性差等特性，以沥青、单质硫粉、导电碳黑和环烷酸镍为原料，通过微波热处理首次实现超快速（30 s）制备S-NiS₂@SP@Bitu硫正极复合材料。NiS₂@SP@Bitu与多硫化物形成Li-N、Li-O、Li-S、Ni-S键，促进载体材料对多硫化物吸附作用，同时降低Li₂S沉积与分解能垒，加速多硫化物的催化转化，从而有效抑制锂硫电池中的“穿梭效应”，电化学性能得到明显提升。在0.5 C倍率下，S-NiS₂@SP@Bitu放电比容量为841.3 mAh g⁻¹，循环500圈后放电比容量仍维持479.6 mAh g⁻¹，载硫量为4.8 mg cm⁻²，电池面容量达到4.6 mAh cm⁻²。该方法利用微波选择性快速加热的优点，创造性地实现制备硫载体材料的同时将硫固定在载体材料中，显著地降低能耗和时耗，为制备硫正极材料开拓新方法。

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