【作者】 李强；

【导师】 陶长元；

【作者基本信息】 重庆大学 ， 工程（化学工程）（专业学位）， 2022， 硕士

【摘要】 金属锰是我国重要的战略金属材料,工业上主要采用电沉积法生产金属锰。锰电沉积过程存在能耗高、电流效率低、阳极泥多等诸多问题。同时,电解过程还存在多重电化学反应耦合的非线性行为,如阳极电势振荡、金属分形生长。非线性行为降低了体系的稳定性,增加额外能耗。因此,寻求高电催化活性的阳极材料,调控电解过程中的非线性行为,是实现电沉积过程节能降耗的关键。本研究通过混沌电路耦合强化电极反应过程,调控阳极振荡行为及产物组成。利用钛氧化物阳极材料替代铅合金阳极,探究电极材料的电化学性能。主要研究内容如下:（1）研究了外控电源对电沉积过程的影响。分别以超混沌电路（Hyperchaotic circuit,HCC）和调幅调频混沌电路（Amplitude modulation and frequency modulation chaotic circuit,AM&FMCC）代替直流（Direct current,DC）,研究了不同电流激励模式对锰电沉积过程的影响。结果表明,HCC和AM&FMCC极化作用下,振荡诱导期分别延后了423 s和134 s,阳极平均振幅降低49 m V,平均振荡频率减小0.234 Hz,相空间吸引子呈扁平的收缩和压缩状态,振荡行为被抑制。此外,混沌电流极化作用下,阳极产物的生成量减少,电极的溶蚀量降低。混沌电流通过电激励信号与内部非线性行为进行耦合作用,调控阳极的电化学行为、阳极产物的表面形貌及组成,进而降低电解能耗。（2）研究了阳极材料对锰电沉积过程的影响。引入一种钛氧化物涂层电极材料（Ti/Ti O_x）作为电解锰过程的阳极,探究了其作为阳极时的锰电沉积情况。结果表明,Ti/Ti O_x电极具有高效的析氧活性,优异的抗腐蚀性能。该电极在硫酸锰溶液中进行电解时,Mn²⁺显示出良好的可逆氧化还原能力,且振荡现象消失。与铅合金阳极相比,其平均阳极电势降低397-510 m V,平均槽压降低97 m V,电流效率提高3.74%,能耗降低8.49%,副产物阳极泥减少79.37%,同时阴极边缘锰颗粒显著减少。Ti/Ti O_x电极的耐腐蚀性和稳定性均优于铅合金电极,电解8 h后,阳极损失量低于0.10%。综上所述,混沌电路非周期性电激励信号与电解体系内部非线性行为耦合,有利于降低由非线性行为引起的能耗。Ti/Ti O_x电极具有优异的电化学性能和稳定性,显著降低了Mn O₂阳极产物的生成,提高了电流效率及金属锰质量,实现了电沉积过程的节能降耗。更多还原

【Abstract】 Manganese metal is an important strategic metal material in our country,mainly produced by electrodeposition in industry.The process of manganese electrodeposition has disadvantages of high energy consumption,low current efficiency and many of anode sludge.At the same time,the electrolysis process also has nonlinear behaviors coupled with multiple electrochemical reactions,such as potential oscillation of anode and fractal growth of metal.The nonlinear behavior reduces the stability of the electrolysis system and increases additional energy consumption.Therefore,seeking anode materials with high electrocatalytic activity and regulating the nonlinear behavior during electrolysis process,which is the key to achieve energy saving and consumption reduction in electrodeposition process.In this work,the electrode reaction process that coupling with chaotic circuit is enhanced,which regulate the anode oscillation behavior and product composition.The electrochemical performance of the electrode material was investigated by replacing the lead alloy anode with titanium oxide anode material.The main research contents are as follows:（1）The influence of externally controlled power supply for the electrodeposition process was studied.The direct current（DC）was replaced by hyperchaotic circuit（HCC）and amplitude modulation frequency modulation chaotic circuit（AM&FMCC）,respectively,and the effects of different current excitation modes for manganese electrodeposition were investigated.The results show that the polarization of HCC and AM&FMCC,the oscillation induction period was delayed by 423 s and 134 s,respectively,the average anode amplitude decreased by 49 m V,and the average oscillation frequency decreased by 0.234 Hz.A flattened and compressed state was showed by the phase space attractor,the oscillatory behavior is suppressed.In addition,under the polarization of chaotic current,the generation of anode products was reduced,and the amount of electrode dissolution was decreased.The chaotic current acted through the coupling of electrical excitation signals with internal nonlinear behavior,regulating the electrochemical behavior of the anode,the surface morphology and composition of the anode product,and thus reducing the electrolytic energy consumption.（2）The effect of anode material on the manganese electrodeposition process was investigated.A titanium oxide coated electrode material（Ti/Ti O_x）was introduced as an anode for the electrolytic manganese process,and the results of manganese electrodeposition was investigated when it was used as the anode.The results shown that the Ti/Ti O_x electrode had efficient oxidation activity and excellent corrosion resistance.The electrode showed excellent reversible redox ability of Mn²⁺when electrolyzed in manganese sulfate solution,and the oscillation phenomenon disappeared.Compared with the lead alloy anode,its average anode potential was reduced by397-510 m V,the average tank pressure was reduced by 97 m V,the current efficiency was improved by 3.74%,the energy consumption was reduced by 8.49%,and the by-product of anode sludge was reduced by 79.37%.Meanwhile,the manganese particles at the cathode edge were significantly reduced.The corrosion resistance and stability of Ti/Ti O_x electrode were better than those of lead alloy electrode,the anode loss was less than 0.10%after 8 h of electrolysis.To sum up,the coupling between non-periodic electrical excitation signal of the chaotic circuit and internal nonlinear behavior of the electrolysis system was beneficial to reduce the extra energy consumption,which caused by the nonlinear behavior.The Ti/Ti Ox electrode had excellent electrochemical performance and stability,it significantly reduced the generation of anode products with Mn O₂,and improved the current efficiency and the quality of metal manganese,it also realized energy saving and consumption reduction in the electrodeposition process.更多还原