酸性体系微观有序结构聚苯胺/无机杂化节能阳极材料基础研究

Research & discovery performance of the energy saving anodic materials has currently become a hot topic for the field of electrowinning nonferrous metal due to the higher anodic overpotential for oxygen evolution, the lower anodic corrosion resistance and lead pollution. The concept of polyaniline based anode was firstly put forward based on the knowledge of organic chemistry, materials, nonferrous metal and electrochemistry. Polyanilinebased anode can reduce the anodic overvoltage, lower corrosion rate and improve the product quality while maintaining the advantages of Pb-Ag alloy anode. The results have confirmed that polyaniline/WC composite materials have better conductivity and catalytic activity than that of the pure polyaniline in the process of electrowinning nonferrous metal. The micro and ordered structure of polyaniline/inorganic hybrid energy saving anode materials will be synthesized by combined with the surface selfassembly and in situ grafted polymerization. The bonded stationary mechanism between conductive polyaniline and inorganic particles will be researched. And the electrical catalytic mechanism and conductive mechanism of energysaving anodic materials will be studied systematically in acid system. So that conductive stability and electrocatalytic activity of the anodic materials will achieve additive or multiplicative synergistic effect in the process of electrowinning nonferrous metal, realizing to achieve lower anodic overpotential for oxygen evolution. This project will powerfully enrich and deepen the basic theory system of hydrometallurgy, break through weaknesses of the traditional lead-based alloy anode materials, open up a new way for saving energy and reducing consumption in the process of the electrowinning nonferrous metal.

针对有色金属电积过程中，阳极耐蚀性差、阴极锌污染和较高的阳极析氧过电位等问题，研究开发性能优异的节能阳极材料已成为热点。本项目在整合有机化学、材料学、有色冶金和电化学等基础上，提出研制聚苯胺基节能阳极材料。该阳极材料具有保持铅银合金阳极优势，同时可显著降低阳极析氧过电位，减少阳极腐蚀并提高阴极产品质量。前期研究工作表明，聚苯胺/WC复合电极材料在锌电积过程具有较好的导电性和催化活性。本项目采用表面自组装和原位接枝聚合相结合技术制备具有微观有序结构的聚苯胺/无机杂化节能复合阳极材料，探讨无机杂化粒子与聚苯胺之间接枝聚合的聚合机理，研究节能阳极材料在酸性体系中的导电机制和电催化机制，以达到导电稳定性和电催化活性相加或相乘的协同效应，以实现较低的阳极析氧过电位为目标。项目极大地丰富和深化了湿法冶金的基础理论体系，突破传统铅基合金阳极材料的缺点，为有色金属电积过程实现节能降耗开辟了一条新途径。

开展的酸性体系微观有序结构聚苯胺/无机杂化节能阳极材料基础研究，本课题通过研究导电聚苯胺复合材料的制备技术，再掺杂具有电催化活性的无机纳米杂化材料，然后经交联流变成型制成导电聚苯胺/无机杂化节能阳极，期望代替传统的有色金属电积过程采用铅基合金阳极。首先通过无机杂化粒子构建导电聚苯胺与无机颗粒之间的化学键，通过电化学特性分析获得材料在酸性体系中的导电机制和电催化机制。其次采用表面自组装和原位接枝聚合相结合技术，研究无机杂化粒子组成、苯胺表面接枝方法、聚合反应条件等对复合阳极的影响规律，确定优化工艺参数，获得微观有序结构的聚苯胺/无机杂化阳极材料制备技术，揭示无机杂化粒子与聚苯胺之间的键合过程，建立复合阳极材料的导电稳定性和电催化性的相关机理及在酸性体系的电极过程动力学特性、析氧电催化机理和导电机制等的基础理论，为实现有色金属电积过程节能降耗奠定基础，最终顺利完成了整体研究目标并取得显著进展。项目资助发表核心论文13篇，录用待刊1篇，培养硕士生5名，其中3名已经取得硕士学位，2名在读。项目投入21万元，支出18.4379万元，各项支出基本与预算相符。剩余经费2.5621万元，剩余经费计划用于本项目研究后续支出。