高倍率氟化铁纳米电极的构筑与电化学性能研究-化学工程与技术专业论文.docxVIP

哈 哈尔滨工业大学工学博士论文 Abs Abstract 万方数据 万方数据 万方数据 万方数据 268.9 m2 g?1，平均孔径尺寸为 5.59 nm，发达的孔道结构和大比表面积保证了电解 液的充分浸润和锂离子的快速传输。FeF3·0.33H2O@CNHs 复合电极材料在 0.5 C、 1 C、2 C、5 C、10 C 和 20 C 的倍率下进行充放电，放电容量分别为 169, 157, 140, 131、120 和 106 mAh g?1。在高达 50 C 的充放电倍率下，复合电极材料依然可以 稳定的释放高达 81 mAh g?1 的容量。在 1 C 的充放电倍率下，50 次充放电循环后 放电容量为 153 mAh g?1。 采用溶剂热合成的方法，制备了具有分等级结构的自支撑 FeF3·0.33H2O 花状 阵列电极，通过分析不同溶剂热反应时间所得样品的微观形貌，研究 FeF3·0.33H2O 花状阵列的生长机理。FeF3·0.33H2O 花状阵列是由 10 nm 厚的―纳米花瓣”相互连 接形成直径约为 1 μm 的分等级花状结构。进一步借助氮气吸脱附测试对花状阵列 的孔径分布进行了分析，样品在 3.5 nm 和 10-20 nm 这两个位置存在着明显的介孔 分布。其中，3.5 nm 的介孔为组成“纳米花瓣”的纳米颗粒之间形成的孔道；而 10-20 nm 的介孔则对应着相邻的“纳米花瓣”之间形成的开放孔道结构。 FeF3·0.33H2O 花状阵列不仅具有高速的电子传输通道，还兼具开放的花状结构、 独特的等级孔道结构和大比表面积，这些独特的结构特点使 FeF3·0.33H2O 电极材 料的电化学性能得到了显著的提高。 关键词：氟化铁；锂离子电池；正极材料；纳米复合材料；电化学性能 - II - Abstract Iron fluoride has attracted a rapidly increasing amount of attention because of its high operating potential, high theoretical capacity of 237 mAh g?1, and relatively low cost. Despite these advantages, the application of iron trifluoride has been limited due to its intrinsic drawbacks, for instance, the slow diffusion of Li+ and low electron conductivity. With regards to the features of iron fluoride, our work develops several new strategies to construct four kinds iron fluoride electrode materials with unique nanostructure. X-ray diffraction, Raman spectrum, Scanning Electron Microscopy, Nitrogen adsorption-desorption techniques, Transmission Electron Microscopy, Discharge/charge measurement and Electrochemical impedance spectroscopy are applied to characterize the physicochemical properties and electrochemical behavior of Li+ insertion/extraction process of the as-obtained iron trifluoride smaples. A tactful ionic-liquid (IL)-assisted approach on in situ synthesis of iron fluoride/graphene nanosheet (GNS) hybrid nanostructures was developed. To ensure uniform dispersion and tight anchoring of the iron fluoride on graphene, we employed an IL which served not only as a green fluoride source for the crystalliz