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物理系统振荡同步的成功实例已经有很多,但电化学系统振荡同步的实例还不多见。为了将用于物理系统振荡同步的方法应用于电化学系统,探索电化学振荡同步的新方法,以铜阳极在磷酸中的电流振荡为研究对象,以自制的电化学联机装置为工具,以铜阳极的电极电位为控制变量,用比例耦合同步方法研究2个独立电解池中铜阳极电流振荡的同步行为。本文的同步方法将比例调节和耦合方法结合起来,是2个电极电流振荡同步的有效算法。比例耦合同步方法的比例系数K为正值时,产生互同步效果;为负数时,产生反相同步效果。当两电极的振荡波形相同时,互同步的效果好;否则,效果差。在能发生电流振荡的电势范围内,铜在磷酸中阳极溶解的电极电位与电极电流之间成反比关系。根据这个反比关系,定性解释了本文方法实现互同步和反相同步的机理。2个互同步的电极电流之差很接近于零,但因为2个铜阳极的表面粗糙度很难完全相同,导致真实的电化学反应面积也很难完全相同,总有余差存在。根据比例调节的特点,用反证法证明余差的存在是本文的互同步方法能够成功实现的前提条件。最后,本文对互同步算法指出了改进的方向。
There have been many successful examples of oscillation synchronization in physical systems, but few examples of oscillation synchronization in electrochemical systems are available. In order to apply the method of oscillation synchronization in physical system to electrochemical system and to explore a new method of electrochemical oscillation synchronization, the current oscillation of copper anode in phosphoric acid is taken as the research object. With the homemade electrochemical on-line device as a tool, The anode potential was used as the control variable. The synchronous behavior of copper anode current oscillations in two independent cells was investigated by the method of proportional coupling synchronization. The synchronization method in this paper combines proportional adjustment and coupling method, which is an effective algorithm for the synchronization of two electrode current oscillations. Proportional coupling synchronization method when the proportionality coefficient K is positive, produce mutual effect; when it is negative, produce anti-phase synchronization effect. When the oscillation waveform of the two electrodes are the same, the effect of mutual synchronization is good; otherwise, the effect is poor. In the potential range where current oscillations occur, the anodic dissolution of copper in phosphoric acid is inversely proportional to the electrode current. According to this inverse relationship, this paper qualitatively explains the mechanism of the method in this paper to achieve mutual synchronization and anti-synchronization. The difference between the two electrode currents is very close to zero. However, since the surface roughness of the two copper anodes is hard to be exactly the same, the real electrochemical reaction area is hard to be exactly the same and there is always a residual error. According to the characteristics of proportional adjustment, the existence of residuals is proved by the negative proofs, which is the prerequisite for the successful implementation of this method. Finally, this paper points out the direction of improvement for the mutual synchronization algorithm.