非贵金属基杂原子掺杂碳纳米管的原位合成及其锌空电池应用

The development of bifunctional oxygen electrodes with low cost, highly active and stability has been considered as a key technology to realize zinc-air batteries commercial applications. This project proposes to build the controllable morphology, composition and structure of non-precious metal based heteroatom-doped carbon nanotubes by using a facile in situ growth strategy. Based on the conditions of as-prepared composites, to clarify the controllable growth mechanism. By fully taking advantage of excellent conductivity, high specific surface area, more active sites of non-precious metal based heteroatom-doped carbon nanotubes, greatly enhancing the intrinsic catalytic activity of the as-prepared composites. Further studying the synergistic catalytic mechanism of the as-prepared catalysts, in order to clarify the internal relation and structure-activity relationship between material preparation, structural control and performance optimization. Eventually, based on such composites served as the corresponding bifunctional oxygen electrode, constructing the high-performance zinc-air batteries. The ultimate aim to achieve the artificial control and performance optimization of the non-precious catalysts with low cost, high catalytic activity and long-term stability, and finally provide theoretical fundament and experimental basis for the development and application of the new-type bifunctional catalytic materials.

研究开发低廉、高效、稳定的双功能氧电极材料是发展锌空气电池的关键技术之一。本项目拟采用原位生长策略，设计合成基于非贵金属粒子诱导生长的杂原子掺杂碳纳米管复合材料。通过对非贵金属基杂原子掺杂碳纳米管实现结构、组成和形态的理性设计与可控制备，可以充分利用金属与碳纳米管高导电性、高比表面积和杂原子诱导的活性位点多等性能优势，从而大大提高复合材料的本征催化活性；深入研究金属基杂原子掺杂的碳纳米管各活性组分之间的协同催化机制，阐明材料制备—结构调控—性能优化之间的内在联系和构效关系；进一步构建以该类催化材料为双功能氧电极的高性能锌空电池。以期实现高催化活性、高稳定性、成本低廉的非贵金属电催化材料的调控及优化目标，最终为新型双功能电催化材料的开发与应用提供理论基础与实验依据。

本项目针对发展锌空气电池开发低廉、高效、稳定的双功能氧电极材料的关键技术难题。采用原位生长策略，设计合成基于非贵金属粒子诱导生长的杂原子掺杂碳纳米管复合材料。通过对非贵金属基杂原子掺杂碳纳米管实现结构、组成和形态的理性设计与可控制备，可以充分利用金属与碳纳米管高导电性、高比表面积和杂原子诱导的活性位点多等性能优势，从而大大提高复合材料的本征催化活性；深入研究金属基杂原子掺杂的碳纳米管各活性组分之间的协同催化机制，阐明材料制备—结构调控—性能优化之间的内在联系和构效关系；进一步构建以该类催化材料为双功能氧电极的高性能锌空电池。.其中，制备的NiCo2O4/NCNTs/NiCo在ORR (E1/2 = 0.83 V)和OER (Ej10 = 1.58 V)两种催化剂中均表现出较好的催化活性，优于工业催化剂Pt/C和IrO2。所组装的Zn-空气电池的测试表明，在充放电586 h期间，具有较小的放电电压间隙和稳定的电压平台。Co3+离子的电子结构与催化性能之间的关系，通过置换惰性阳离子Zn，构筑了ZnxCo3-xO4基尖晶石并探究了其在氧催化活性。将氮掺杂空心多孔碳球(NHCS)与活性ZnxCo3-xO4偶联，Zn0.6Co2.4O4/NHCS表现出优异的氧催化活性。由ZnCo取代引起的Co-O键长变化也会影响键的共价性。在OER过程中，八面体环境的改变有利于Co-OOH•中间产物的形成。基Zn0.6Co2.4O4/NHCS的组装式锌空气电池开路电压高(1.47 V)，功率密度大(136 mW cm-2)，充放电稳定时间为120 h。.实现了高催化活性、高稳定性、成本低廉的非贵金属电催化材料的调控及优化目标，最终为新型双功能电催化材料的开发与应用提供理论基础与实验依据。同时拓展了相关材料多功能应用领域、如：电催化制氢/制氧、电催化尿素分解、光电催化等。项目实施期间超额完成项目预期目标，以第一作者和通讯作者身份总共发表高水平 SCI 论文66篇。