面向全钒液流电池MnxOy电催化剂的可控合成及其催化机理研究

全钒液流电池在大型储能领域有着广阔的应用前景，然而，低电化学活性的电极材料限制了全钒液流电池的发展。为此，本项目拟采用非贵金属锰系列氧化物MnxOy代替贵金属作为钒电对电催化剂，采用电沉积法在碳基电极表面负载MnxOy。通过控制碳基材料预处理、添加剂种类、沉积方式、沉积温度等因素在材料表面直接沉积具有不同形貌和物相的MnxOy，以便研究晶体结构、化学组成、形貌、生长取向对正、负极钒电对电化学性能的影响，进一步建立MnxOy物相、形貌与钒电对电催化性能的构效关系。通过深入的晶体结构和价键分析，总结MnxOy对电极反应的促进作用，从内、外扩散两方面研究钒离子在不同形貌材料上的扩散特性；最终从电极表面反应和扩散过程两方面揭示MnxOy对正、负极钒电对的催化作用机理。本项目对全钒液流电池电催化材料的合成和理论发展有重要意义，为新能源进一步应用提供关键理论参考和技术支撑。

Vanadium redox flow batteries has broad application prospect in large-scale energy storage field. However, the low electrochemical activity of electrode material limits the development of vanadium redox flow batteries. Therefore, this project intends to adopt a series of non-precious metal manganese oxide MnxOy insteading of precious metals as electrochemical catalyst for vanadium couples, depositing MnxOy on carbon-based electrode surface by electrodeposition method. The MnxOy with different morphology and phase can be deposited by controlling the condition such as pretreatment of electrode materials, kind of additives, deposition method, temperature and other factors, for investigating the effect of crystal structure, chemical composition, morphology, growth orientation on the electrochemical performance of the positive and negative vanadium couples, and then establish the relationship between the phase, morphology and catalytic properties of vanadium couples. The promotive effect of MnxOy could be summarized by analysis of the crystal structure and the valence bond, and the effect of the morphology of different materials on the diffusion process of vanadium ions could be investigated from internal diffusion and external diffusion. Finally, the catalytic mechanism of vanadium positive and negative vanadium couples coule be exposited from electrode reaction and diffusion process. The project has great significance on the synthesis and theory development of catalytic materials for vanadium redox flow batteries, providing critical theory reference and technical support for further application of new energy.