锌电积用3D钛基β-PbO2-MnO2复合电极的制备、性能及机理研究

The phenomenon of the utilization of the high chloride zinc concentrate and the zinc oxide which lead to dramatic reduction of the production, economic and technical index has been paid much attention in zinc electrowinning. Research on the preparation of a kind of long-life, energy saving fence-like 3D Ti substrate β-PbO2-MnO2 composite electrode as well as its performance and mechanism will be carried out to overcome the disadvantage of lead substrate alloy anode used in zinc electrowinning. Main research contents of the project include the following aspects:(1) the effect of different process conditions (such as pretreatment, thermal decomposition, composite electrodeposition, etc) on the performance of various oxide film will be studied; (2)the reaction mechanism of composite electrodeposition will be also researched; (3) the electron transfer law on each coating of the anode used in electrolyte will be studied; (4) the influence of the lattice distortion on the internal stress will be also analyzed; and (5) the electrochemical behavior, performance indexes as well as the breakage mechanism of the anode material in zinc electrolyte will be studied. The oxygen evolution dynamic model of the active layer will be established. The key problem to be resolved in this project is the differences of the bonding mechanism of the interface among the oxide film and the electrochemical mechanism of action of each component of the anode material used in zinc electrolysis. The research of the project will greatly enrich and deepen the basic theory of the application on anode used in hydrometallurgy. It also provides theoretical basis and technological support for the major problems such as high energy consumption and the low quality of the zinc cathode. In addition, we can find a new phenomenon and new laws, which will enrich our understanding about the anode material for non-ferrous electrolyte.

锌电积面临高氯锌精矿以及锌氧粉的运用而造成生产经济技术指标严重下滑的现象已引起行业内高度重视。针对现有锌电积用铅基合金阳极的不足之处提出了开展一种耐久性节能新型栅栏型3D钛基β-PbO2-MnO2复合电极的制备、性能及机理研究。主要研究不同工艺条件（如前处理、热分解、复合电沉积等）对各种氧化物膜的性能影响规律以及复合电沉积的反应机理，阳极在应用过程中各涂层电子传递规律和晶格畸变对内应力的影响规律。探讨阳极材料在锌电解溶液中的电化学行为、性能指标和阳极破损机理，建立活化层各组分在电解液中的析氧动力学模型。重点解决各氧化膜之间的界面匹配差异和阳极材料中各成分在锌电解中的电化学作用机理。该项目研究将极大地丰富和深化阳极在湿法冶金应用基础理论体系，对锌冶金行业中面临的高能耗和低品质锌的重大难题提供理论依据和技术支撑。通过本项目的研究还可能发现新现象和新规律，丰富人们对有色电解中的阳极材料的新认识。

本项目针对现有锌电积用铅基合金阳极的不足之处提出了开展一种耐久性节能新型栅栏型3D钛基β-PbO2-MnO2复合电极的制备、性能及机理研究。采用热分解和电沉积方法制备了各种氧化物膜并进行了性能研究，发现了阳极在应用过程中各涂层电子传递规律。探讨了阳极材料在锌电解溶液中的电化学行为、性能指标和阳极破损机理，建立了活化层各组分在电解液中的析氧行为，考察了锌电积模拟实验中新型阳极材料的槽电压、电流效率、电耗、腐蚀速率等经济技术指标，取得的主要研究结果如下：.(1)对金属钛前处理的腐蚀，腐蚀最严重的是20%H2SO4，其次是20%HCl，最弱的是10%H2C2O4。盐酸浓度的增加，基体孔数量增多和扩大。.(2) 随着Ru含量的增大，钛基锡锑钌电极表面块状结构逐渐变大，裂纹变少变浅；随着煅烧温度的增加，电极表面的裂纹逐渐变深变大；且Ru和Sb活性氧化物的量的比例随Ru的增加而增加。.(3) 重铬酸钾的加入对α-PbO2镀层形貌有明显的影响，可以使晶粒大小更加均匀，在添加量到达2%时，制备的电极使用效果最佳。.(4) Fe3+掺杂到镀液中，阴极表面析铅反应被抑制，并减弱了电极的边缘效应，使得制备得到的β-PbO2层晶粒均匀致密。硝酸银的加入可以使β-PbO2镀层晶粒逐渐增大，使获得的二氧化铅沉积速率快，提高了二氧化铅的活性和导电性，与表面形貌无关。.(5) 在Ti/Sn-Sb-RuOx电极上易形成多孔PbO2镀层。Ru对作用在于能形成大量的氧气泡。氧气和二氧化铅在阳极表面相互竞争形成多孔层，降低β-PbO2内应力的作用。.(6) 在多孔二氧化铅表面电沉积制备锰钌氧化物，易形成梯度固溶体，得到的Ti/Sn-Sb-RuOx/ β-PbO2/MnO2-RuO2梯度阳极，相对Pb-0.8%Ag电极，在相同的条件下电解锌，槽电压降低约0.4V，能耗减少11%，节能效果显著；在含2g/L氯离子的硫酸溶液中以1 A/cm2电流密度强化寿命达到95 h，寿命明显高于铅合金电极。.(7) 获得省部级奖三项，一等奖1项，三等奖2项；发表学术论文29篇，其中SCI收录期刊13篇，出版专著1部；获得国内授权发明专利8件，国外授权发明专利2件，申请发明专利3篇；培养研究生6人，国内做学术报告4次，参加国际学术会议2次。