钼基复合氧化物/石墨烯的纳米结构可控构筑及储锂性能研究

The properties of functional nanostructured assemblies can be finely tuned by controlling the component, structure, morphology, surface/interface, and arrangement of their building blocks. They hold a great potential for the design and application of energy-storage devices. This project is mainly focused on the development of novel nanostructured anode materials for the next-generation power and energy-storage Li-ion batteries (LIBs). The hybrid nanostructures comprising Mo-based composite oxides and graphene will be controllably fabricated, and will be used as anode materials with high capacity, high rate capability, and long cycle life. The controlled growth and formation mechanism of the nanostructures and nanoarchitectured assemblies will be explored. The dependence of the capacity,rate capability,and cycle life on the component, structure, morphology of the hybrids will be investigated systematically. The synergistic effect of the building blocks will be explored on the base of both the experimental and the theoretical results. The relationship between the microstructure/nanostructure and the lithium-storage performance together with the evolution rule will be clarified. Furthermore, we will explore the processes of the electron conduction and Li-ion diffusion during the discharge/charge reactions, facilitating the controlled synthesis and future use of the high-performance anode materials in LIBs. It is expected that this research would not only provide beneficial guidance and help to next-generation high-performance LIBs, but also lay the scientific foundations for developing advanced energy transfer and storage systems, thus promoting the discipline cross and fusion of chemistry, materials,energy, and etc.

功能纳米组装体的性质可以通过改变"建筑单元"的组分、结构、形貌、表面/界面和排列方式进行精确调控，这在储能器件设计与应用方面具有诱人的应用前景。本项目旨在研发一系列高性能下一代锂离子动力与储能电池新型负极材料，可控构筑结构稳定且具有高能量密度、高倍率充放电性能和长期循环性能的钼基复合氧化物/石墨烯纳米复合材料。探索纳米结构与纳米组装体的可控生长与形成机制，系统研究纳米复合物的组分、结构、形态对其比容量、倍率性能、循环寿命的影响，在实验和理论结合的基础上认识纳米组装体"建筑单元"的协同效应，揭示微/纳米结构与储锂性能的构效关系与演变规律，探索新型电极材料在电化学反应过程中电子传导、锂离子扩散的相关机理，实现高性能锂离子电池负极材料的可控制备与应用。为开发高性能下一代锂离子二次电池提供有益的指导与帮助，为先进能量转换与储存技术的发展奠定科学基础，促进化学、材料、能源等学科的交叉融合。

本项目通过自组装法、溶液反应、静电纺丝法结合热处理可控构筑了Mn2Mo3O8/石墨烯、Fe2Mo3O8/石墨烯、MoO3-x/C类电极材料，并优化制备条件，对电极的材料组成、结构、形貌等进行了表征，对电池电化学性能进行了测试，并提出了相关机理。含钼化合物及其纳米复合物的储锂机制与储钠机制类似，在完成本项目研究内容的基础上，我们进一步探索了含钼化合物的储钠特性。此外，还还开展了其他碳基材料/过渡金属氧（硫化物）化物纳米复合材料的制备与储锂性能研究：(i) 柔性MoS2/C纳米纤维薄膜钠离子电池负极材料及其储钠特性；(ii) 高容量、长寿命ZnO/ZnFe2O4/C纳米复合负极材料及其储锂性能研究；(iii) Sb/C复合电极材料、柔性 Sb-rGO、NVP-rGO复合电极材料与柔性电池。本项目研究实现长寿命大倍率锂离子电池钼基氧化物负极材料及其过渡金属氧化物/硫化物的可控制备，为开发高性能下一代锂离子二次电池提供有益的理论指导与技术支持，对促进先进电化学储能材料与器件的发展具有重要的意义。标注该项目资助的SCI学术论文共50篇。所发表论文受到了国内外同行的广泛关注，入选基本科学指标数据库（ESI）高被引论文 8 篇（Chem. Soc. Rev. 1 篇、Nat. Commun. 1 篇、Sci. Rep. 1 篇、Adv. Mater. 1 篇、Adv. Funct. Mater. 1 篇、ACS Appl. Mater. Interfaces 1 篇, Nanoscale 1篇，Nano Lett. 1篇），其中 1 篇（Nat. Commun. 2015, 6, 6929）入选 2015年“中国百篇最具影响国际学术论文”。申请中国发明专利2项（其中授权专利1项）。该项目所取得的成果（Adv. Funct. Mater. 2013, 23, 2436）作为重要研究成果之一，获得了国家自然科学二等奖1项、教育部自然科学一等奖1项。