A novel approach to analyze electrochemical impedance spectroscopy (EIS), based on evolutionary programming, has been utilized to characterize supercapacitors operation mechanism and degradation processes. This approach poses the ability of achieving a comprehensive study of supercapacitors via solely AC measurements. Commercial supercapacitors were examined during accelerated degradation. The microstructure of the electrode-electrolyte interface changes upon degradation; electrolyte parasitic reactions yield the formation of precipitates on the porous surface, which limit the access of the electrolyte ions to the active area and thus reduces performance. EIS analysis using Impedance Spectroscopy Genetic Programming (ISGP) technique enables identifying how the changing microstructure is affecting the operation mechanism of supercapacitors, in terms of each process effective capacitance and time constant. The most affected process is the transport of electrolyte ions at the porous electrode. Their access to the whole active area is hindered, which is shown in our analysis by the decrease of the capacitance gained in the transport and the longer time it takes to penetrate the entire pores depth. Early failure detection is also demonstrated, in a way not readily possible via conventional indicators. ISGP advanced analysis method has been verified using conventional and proven techniques: cyclic voltammetry and post mortem measurements.

中文翻译：

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超级电容器退化表征的新方法

基于进化规划，一种用于分析电化学阻抗谱（EIS）的新颖方法已被用来表征超级电容器的工作机理和降解过程。这种方法具有仅通过交流电测量就可以对超级电容器进行全面研究的能力。在加速降解期间检查了商用超级电容器。电极-电解质界面的微观结构会随着降解而改变；电解质的寄生反应会在多孔表面上形成沉淀，这会限制电解质离子进入活性区域，从而降低性能。使用阻抗谱遗传规划（ISGP）技术进行的EIS分析能够确定不断变化的微观结构如何影响超级电容器的运行机制，在每个过程中有效电容和时间常数。影响最大的过程是电解质离子在多孔电极上的传输。它们进入整个活性区域受到了阻碍，这在我们的分析中得到了体现，即在传输过程中获得的电容减小，并且穿透整个孔深度所需的时间更长。还显示了早期故障检测，这是通过常规指示器无法轻易实现的。ISGP先进的分析方法已使用常规和行之有效的技术进行了验证：循环伏安法和验尸测量。在我们的分析中，这可以通过减少运输过程中获得的电容以及穿透整个孔隙深度所需的时间来证明。还显示了早期故障检测，这是通过常规指示器无法轻易实现的。ISGP先进的分析方法已使用常规和行之有效的技术进行了验证：循环伏安法和验尸测量。在我们的分析中，这可以通过减少运输过程中获得的电容以及穿透整个孔隙深度所需的时间来证明。还显示了早期故障检测，这是通过常规指示器无法轻易实现的。ISGP先进的分析方法已使用常规和行之有效的技术进行了验证：循环伏安法和验尸测量。