二维卟啉金属有机框架纳米材料的可控制备及其在电化学储能器件上的应用研究

As a newly developed material, the two-dimensional (2D) metal−organic framework (MOF) nanosheet, a new member of the 2D material family, has been a research hotspot in the field of nanomaterials. One challenging work is to realize the controllable synthesis of 2D MOF nanosheet and its application in electrochemical energy storage devices. In this work, we mainly investigate the science and technology of the preparation of 2D metalloporphyrinic MOF nanosheet, as well as its applications as electrode materials for lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), supercapacitors (SCs), and as separators in lithium-sulfur (Li-S) batteries. It is expected to establish the controllable 'bottom-up' pathways for the synthesis of 2D metalloporphyrinic MOF nanosheet with the aid of surfactants, as well as to explore the main factors affecting the composition, morphology and thickness of the as-synthesized 2D MOF nanosheet. The applications of the 2D metalloporphyrinic MOF nanosheets in electrochemical energy storage devices will also be studied. Based on the ion sieve nature and 2D characteristics of the MOF, one application is used as the separator in Li-S battery to prevent the ‘shuttle effect’ of Li2Sx, thus improve the cycling stability and enhance the energy density. The other one is to synthesize 2D high-performance hybrid electrode materials for LIBs, SIBs and SCs basing on the template nature of the 2D MOF nanosheets, and uncover the functions of nano-carbon and nano-metal derivatives in these 2D nanocomposites.

作为二维材料家族的新成员，二维金属有机框架纳米材料（Metal-Organic Framework，MOF）是当今纳米材料领域的研究热点之一。如何实现高效可控的二维MOF纳米材料的制备并探索其在电化学储能器件上的应用是一项具有挑战性的工作。本项目主要研究二维卟啉MOF纳米材料的制备科学与技术，及其在锂（钠）离子电池、超级电容器电极材料与锂-硫电池隔膜上应用的基础问题。拟针对二维卟啉MOF纳米材料发展表面活性剂辅助的“自下而上”的可控制备方法，探明影响其结构、形貌、厚度的主要因素。借助二维卟啉MOF的“离子筛”功能和二维特性，探索其对Li2Sx “穿梭效应”的抑制作用，实现锂-硫电池隔膜的应用，提高电池的循环稳定性和能量密度。利用二维卟啉MOF的功能化模板结构特征，制备性能优异的二维纳米复合电化学储能材料，揭示其中纳米碳骨架和纳米金属衍生物的结合机理和相互作用规律。

二维金属有机框架材料（MOF）纳米材料，具有高比表面积、丰富的配位不饱和的金属位点等独特性质，是当今纳米材料领域的研究热点之一。如何实现高效可控的二维MOF纳米材料的制备并探索其在电化学储能器件上的应用是一项具有挑战性的工作。. 本项目通过表面活性剂辅助制备的方法合成了Co-MOF、Cu-MOF、Co-(Fe)MOF等系列二维金属卟啉MOF纳米片材料并探索了制备规律，实现了在锂-硫电池、电催化析氧反应和电化学检测等中的高效应用。在锂-硫电池体系中，在传统PP隔膜的正极侧修饰Co-MOF有效抑制多硫化物穿梭并提高电池比容量; 在PP隔膜负极侧修饰Cu-MOF不仅可以抑制多硫化物的穿梭效应，而且可以使Li+通量均匀，诱导锂的均匀沉积。二维Cu-MOF/MWCNT复合膜修饰的电极可用H2O2的电化学检测，在较宽的浓度范围内，具有低检测限和高灵敏度，并可应用于血清和啤酒中的H2O2含量的检测。使用双金属Co-(Fe)MOF作为模板前驱体，通过碳化和磷化处理，得到铁掺杂的CoP纳米颗粒均匀分散在碳基体（Fe-CoP/C）形成的复合纳米片，该复合材料在1 M KOH电解液中表现出优异的OER性能。纳米片状形貌、导电碳框架以及铁掺杂协同提升了OER反应活性。