二维金属有机框架衍生的阵列化碳/金属氮化物复合材料和柔性锌空气电池研究

In order to achieve both high energy storage properties and high mechanical properties for flexible energy storage devices, this project will rationally design a carbon/metal nitride hybrid nanoarrays for flexible Zn-air battery, by utilizing a two-dimensional metal-organic framework nanoarrays as the precursor. A facile and economic thermal treatment will be utilized to transform the precursor into a low-cost carbon/metal nitride hybrid binder-free electrode, which can achieve similar or even better electrochemical properties compared with noble-metal based materials, resulting in a flexible solid-state Zn-air battery with excellent electrochemical and mechanical properties. This project will focus on the research of the heat treatment conditions, especially the parameters during the nitridation process, and its connection with the morphology and growth mechanism of carbon/cobalt nitride, their microstructure and interfacial properties, as well as the oxygen evolution and reduction properties in electrochemical test. The influence factors on the properties of the Zn-air battery, such the nitridation process, the synergistic effect between the carbon and cobalt nitride and the effect of the binder-free electrode, will be systematically investigated, which will pave way for the rational improvement of the electrochemical and mechanical properties . With these efforts, the project will obtain a flexible Zn-air battery with high energy density, high power density and good stability; In addition, the Zn-air battery can be also mechanically bend, rolled and folded. In all, the project will provide new theoretical and experimental support for the controllable synthesis of high-performance carbon/metal nitride composite electrode materials, explore the deeper applications of metal-organic frameworks nanoarrays in energy storage, and achieve a significant guidance for the realization of the next-generation flexible energy storage devices with excellent electrochemical and mechanical properties.

根据对柔性储能器件的储能性能和机械性能的要求，本项目以二维金属有机框架阵列为前驱体，通过经济简便的加热处理方法，构建阵列化的碳/金属氮化物复合电极材料，获得接近或优于贵金属的电化学性能，最终实现储能性能和机械性能优异的柔性锌空气电池。本项目将重点研究不同热处理条件下，尤其是氮化过程中纳米氮化钴的形貌和生长机理、多孔碳/纳米氮化钴复合电极的微观组织结构及界面性能、以及该复合材料在氧氧化和氧还原中的电化学性能，阐明氮化时间温度、碳/氮化钴的协同作用、无粘结剂电极结构等因素对改善锌空气电池电化学性能和机械性能的影响，并实现高能量密度、高功率密度、循环稳定且可弯曲、卷曲、折叠的柔性锌空气电池。本项目将为实现可控合成高性能无粘合剂的碳/金属氮化物复合电极材料提供新的理论和实验依据，为阵列化金属有机框架在能源储存上的深入应用做探索，对实现储能性能和机械性能优异的下一代柔性储能器件有重要的指导意义。

由于化石燃料的迅速枯竭及其燃烧造成的不断恶化的污染，当今世界正面临着能源短缺和环境破坏的严峻挑战。高效清洁能源的存储对实现“碳达峰碳中和”目标，有至关重要的作用。开发能量密度高、功率密度高和循环性能好的电化学储能器件是一项刻不容缓的重要任务。锌空气电池是一种由金属锌和空气之间的电势差产生电能的电化学储能装置，被公认为是安全系数高的金属-空气电池。设计并组装新型碳/金属氮化物复合材料作为高性能柔性空气电极，是实现储能性能优异和机械性能优异的柔性锌空气电池的一种有效途径。然而，目前对纳米阵列化、无 粘合剂的金属有机框架前驱体和其衍生物的研究，尤其对其衍生的阵列化碳/ 金属氮化物材料的研究和对其在柔性储能器件的应用研究都还很少。.通过本项目研究，以在柔性衬底上生长二维金属有机框架阵列的前驱体，通过碳化氮化处理，将其转化为碳/金属氮化物的阵列化复合材料。通过简单的硒化处理，制备了碳布支载的具有三维多级结构的硒化钴-氮掺杂碳复合三角片阵列，获得了性能出色的柔性复合电极的制作策略；通过力学建模分析等理论指导，结合计算机辅助设计出构型最优化与效率最大化柔性集流体模型，实现可控合成高性能碳基复合电极材料；通过线扫描法、循环伏安法、交流阻抗法等电化学分析手段系统地研究储能器件的电化学反应机理，获得储能性能和机械性能优异的柔性镍铁电池；以密度泛函理论计算模拟为指导，提出在石墨烯表面引入的含锌基团的方法，实现了锌的均匀分布，有效抑制的锌枝晶的形成；通过优化的压印微图案可诱导锌离子浓度分布结合良好的亲锌层，获得柔性锌负极循环性能的提升的通用策略。因此，本研究的结果为碳基复合电极材料的简易化制备、表面修饰提升性能和高性能柔性储能器件的开发提供了有意义的借鉴依据。.相关研究结果已申请中国发明专利2项，在SCI期刊以上发表16篇SCI论文，其中一区论文15篇，包括Advanced Materials、Nano Letters、ACS Nano、Advanced Functional Materials、Energy Storage Materials等专业领域顶级期刊7篇。