基于金属铁锈蚀反应可控构筑卷绕式FeRx(R=O,P)@rGO复合材料机理及其储锂/钠研究

Based on the concept of material metallurgy, the preparation of high-performance Li/Na ion battery materials from metal or metal minerals via a short process is the intersection and frontier of hydrometallurgy, green chemistry and nano energy. Based on the rusting reaction of metallic iron, this project proposes a new method of “collaborative corrosion-induced scrolling” to controllably construct iron compound/graphene (FeRx@rGO) anode material with a scroll structure. That is, using the synergistic strengthening of rusting reaction by graphene oxide (GO) and ammonium sulfate, the two-dimensional FeOx@GO precursor is efficiently and controllably prepared, and then the two-dimensional precursor will undergo an induced scrolling technique to form scrolled anode material. The process of preparing FeOx on the surface of GO is studied, and the synergistic rust mechanism of metallic iron is explained. The induced scrolling technique of two-dimensional precursor is developed, and the formation mechanism and law of self-scrolling are revealed. And the mechanism of construction of scroll structure on the Li/Na storage properties of FeRx is clarified. This project can not only realize the development of new technology to prepare the composite of graphene and iron compound, but also realize the new concept of composite material in structural design. With the construction of the scroll structure, based on the function of different metal compounds, this project will provide basic research for the development of new graphene-based composite materials, which has important academic value and practical significance.

基于“材料化冶金”理念，直接从金属或金属矿物出发短流程制备高性能锂/钠离子电池材料是湿法冶金、绿色化学和纳米能源领域的交叉和前沿。本项目基于金属铁的锈蚀反应，提出“协同锈蚀-诱导卷绕”新方法可控构筑卷绕式铁化合物/石墨烯（FeRx@rGO）负极材料的设想，即利用氧化石墨烯（GO）和硫酸铵对锈蚀反应的协同强化作用，实现二维FeOx@GO前驱体的高效制备；继而采用硫酸铵诱导法将前驱体制成卷绕式负极。研究在GO表面可控负载FeOx的方法，阐释锈蚀反应的协同强化机制；开发二维前驱体的诱导卷绕策略，揭示自卷绕的形成机理及规律；阐明石墨烯卷绕结构增强FeRx材料储锂/钠性能的作用机理。本项目不仅能够开发石墨烯与铁化合物复合的新技术，而且能够实现复合材料在结构设计上的新理念。借助卷绕式结构的构筑，基于不同金属化合物的功能，本项目将为新型石墨烯复合材料的开发奠定研究基础，具有重要的学术价值和实际意义。

本项目结合湿法冶金、绿色化学、纳米能源等领域的相关理论和研究方法，借鉴“材料化冶金”理念设计构筑卷绕结构石墨烯与铁基化合物复合负极材料，充分发挥卷曲结构石墨烯空间限域和异质化合物优异电化学性能的协同优势。项目提出了一种新颖的方法设计制备石墨烯/FeOx复合材料，研究了材料的制备过程、形成机理、形貌结构演变及调控原理、协同机制，并进一步拓展了碳限域金属化合物的新型复合结构。重点研究了硫酸盐模板法诱导构筑卷绕结构石墨烯及机理、金属铁液相锈蚀反应构筑卷曲结构3D-rGO/Fe3O4复合材料机理及性能调控、“空间限域-异质结构”协同提升Fe3O4/FeS与碳复合负极材料的电化学性能机理等，获得了制备卷绕结构石墨烯复合材料的普适性方法，建立了石墨烯复合电极材料的结构调控策略和性能优化方案。本项目的研究结果将为实现从金属或金属矿物出发，短流程制备卷绕结构石墨烯改性金属化合物新型复合电极材料提供实验基础和理论借鉴。