电负性客体填充的新型方钴矿材料合成和输运机制研究

方钴矿基包合物材料是最具应用前景的中温热电材料之一，其热电优值的提高和规模化可控制备是国际热电材料领域的挑战性难题。本项目基于申请者最新发现的以S、Cl等电负性原子为填充客体的方钴矿材料，结合传统电正性金属原子填充成果，系统研究并揭示不同客体组合填充及置换对方钴矿基材料显微结构、电子结构、客体-主体成键特性和热振动模式等的影响规律，阐明多元填充客体及置换原子的组合规律及其对电热输运行为的影响规律，探索并发展新型多元客体填充方钴矿材料的低能耗规模化可控制备方法和工艺，设计并制备基于电负性客体填充且稳定存在的系列新型方钴矿材料，实现基于多元客体填充方钴矿材料中电、热输运行为的协同调控，为大幅提高p型和n型方钴矿材料的热电优值和材料的规模化制备提供新的途径。

The skutterudite-based inclusion compounds are one of the most promising thermoelectric materials in the intermediate temperature range. How to improve their thermoelectric performance and develop the large-scale preparation technology still remain challengeable so far. Based on our recently findings on electronegative guests (S, Cl etc.) filled CoSb3 skutterudites and previously achievements on electropositive metal atoms filled skutterudites, this project will study and clarify the influence of different filling guests and/or substitutional atoms on various properties of skutterudites, such as the crystal structure, electronic structure and phonon scattering mechanism, thus to reveal the combination law between electronegative guests and substitutional atoms, as well as the electrical and thermal transport characteristics. This project will explore and develop the controllable technology for the large-scale preparation of multiple-guests filled new skutterudites materials with low energy consumption, design and fabricate a series of new stable skutterudites based on the filling of electronegative guests, and realize the synergistic optimization of the electrical and thermal transport characteristics. This research provides a new strategy for developing high-performance bulk p-type and n-type skutterudite materials and their large-scale preparation.