Regulation of anodic potential oscillation in manganese metal electrolysis by hyperchaotic current
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摘要: 金屬錳濕法電冶過程是一個典型的遠離平衡態的非線性體系，直流作用下會出現電化學振蕩、金屬分形等非線性行為而引發體系額外的能耗。本文提出一種超混沌電流電解的新模式，通過引入超混沌電路代替原有直流電源來實現。超混沌電流作用下，采用恒電流極化曲線、陽極極化曲線、塔菲爾測試等分析方法和X射線衍射分析、掃描電子顯微鏡的表征方法，研究鉛合金陽極電化學振蕩行為與陽極沉積的錳氧化物之間的關聯。研究結果表明，在電流密度為350 A·m?2恒電流極化30 min后，超混沌電流極化作用下電位振蕩的平均振蕩周期較直流極化提高5.6 s，平均振幅降低 38 mV；超混沌電流作用下陽極生成的MnO2，其表面較為致密平整，在一定程度上可以提高鉛合金陽極析氧反應活性和耐腐蝕性。綜合分析可知，將超混沌電流運用于金屬錳電解過程，可以實現對陽極電化學振蕩的有效調控，為進一步降低電解過程能耗和污染排放提供新思路。Abstract: Manganese metal electrolysis is a typical nonlinear system far from the equilibrium state. In this case, nonlinear behaviors such as electrochemical oscillation and metal fractal occur in the electrode reaction process. The multiple valence state changes of manganese and the nonlinear coupling of multiple chemical reactions cause the electrolytic process to be unstable and unmanageable, and increase extra energy consumption. Therefore, a study regarding the physical and chemical processes of the electrode/solution interface will help in revealing the electrode reaction mechanism and elaborate the nonlinear behaviors of the interface reaction process. This should control the electrode reaction process more effectively and regulate the entire process more efficiently. This paper presents a new mode of chaotic current electrolysis by introducing a hyperchaotic circuit instead of the original direct current power supply. Galvanostatic polarization, anode polarization, the Tafel test, X-ray diffraction, and scanning electron microscopy were employed to analyze the relationship between the electrochemical oscillation behavior and anodic deposited manganese oxides on lead alloy anodes. Research results show that the potential oscillation behavior of the anode is suppressed to a certain extent. The average oscillation period was increased by 5.6 s, and the average oscillation amplitude was reduced by 38 mV compared with direct current polarization after 350 A·m?2 constant current polarization for 30 min. This would help to reduce the generation of anode slime and additional energy consumption during electrolysis. At the same time, the deposited MnO2 on the anode under hyperchaotic current had a dense and flat surface, which improved the oxygen evolution reaction activity and the corrosion resistance of the lead alloy anode. The comprehensive analysis demonstrated that the application of hyperchaotic current to manganese metal electrolysis could achieve effective regulation of anode electrochemical oscillation, providing a new insight for the further reduction in the energy consumption and pollution emission in the electrolysis process.
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圖 1 系統（1）的混沌吸引子（當 a = 4.5, b =5.5, c =5, d = 4, e = 0.4, m = 1, k = 0.2, 初始值為（1, 0, 1, 0））。（a）x?y；（b）x?z；（c）y?z；（d）x?u
Figure 1. Chaotic attractor of system (1) (a = 4.5, b = 5.5, c = 5, d = 4, e = 0.4, m = 1, k = 0.2, the initial value is (1, 0, 1, 0)): (a) x?y; (b) x?z; (c) y?z; (d) x?u
圖 3 鉛合金陽極的恒電流極化曲線（直流），（b,c）為（a）的局部放大圖
Figure 3. Galvanostatic polarization of lead alloy anode (direct current), (b,c) is a local enlargement of (a)
圖 4 鉛合金陽極的恒電流極化曲線（超混沌電流），（b,c）為（a）的局部放大圖
Figure 4. Galvanostatic polarization of lead alloy anode (hyperchaotic current), (b,c) is a local enlargement of (a)
圖 5 鉛合金陽極電勢振蕩周期的變化情況
Figure 5. Periodic variation of the potential oscillation of lead alloy anode
圖 6 鉛合金陽極電勢振蕩振幅的變化情況
Figure 6. Amplitude variation of the potential oscillation of lead alloy anode
圖 7 不同恒電流極化時間下鉛合金電極的陽極極化曲線
Figure 7. Anodic polarization curves of lead alloy electrodes under different galvanostatic polarization times
圖 8 不同恒電流極化時間下鉛合金電極的塔菲爾曲線
Figure 8. Tafel plots of lead alloy electrodes under different galvanostatic polarization times
圖 10 陽極沉積MnO2的掃描電鏡圖。（a）直流；（b）超混沌電流
Figure 10. SEM images of anodic deposited MnO2: (a) direct current; (b) hyperchaotic current
表 1 不同恒電流極化下鉛合金電極的耐蝕情況
Table 1. Corrosion parameters of lead alloy electrodes under different galvanostatic polarization
Polarization conditions jcorr/(10?4A·cm?2) Ecorr/V 0 min 0.644 0.476 DC, 30 min 1.814 0.476 DC, 60 min 1.908 0.578 HCC, 30 min 1.318 0.505 HCC, 60 min 1.698 0.593 
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