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Distribution of Characteristic Times: A High-Resolution Spectrum Approach for Visualizing Chemical Relaxation and Resolving Kinetic Parameters of Ionic-Electronic Conducting Ceramic Oxides

机译:特征时间的分布:一种可视化化学弛豫和解离子电导陶瓷氧化物的高分辨率谱方法

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摘要

Surface exchange coefficient (k) and bulk diffusion coefficient (D) are important properties to evaluate the performance of mixed ionic-electronic conducting (MIEC) ceramic oxides for use in energy conversion devices, such as solid oxide fuel cells. The values of k and D are usually estimated by a non-linear curve fitting procedure based on electrical conductivity relaxation (ECR) measurement. However, the rate-limiting mechanism (or the availability of k and D) and the experimental imperfections (such as flush delay for gaseous composition change, τf) are not reflected explicitly in the time–domain ECR data, and the accuracy of k and D demands a careful sensitivity analysis of the fitting error. Here, the distribution of characteristic times (DCT) converted from time–domain ECR data is proposed to overcome the above challenges. It is demonstrated that, from the DCT spectrum, the rate-limiting mechanism and the effect of τf are easily recognized, and the values of k, D and τf can be determined conjunctly. A strong robustness of determination of k and D is verified using noise-containing ECR data. The DCT spectrum opens up a way towards visible and credible determination of kinetic parameters of MIEC ceramic oxides.
机译:表面交换系数(k)和批量扩散系数(d)是评估混合离子电子导电(MiEC)陶瓷氧化物用于能量转换装置的性能的重要性质,例如固体氧化物燃料电池。 K和D的值通常通过基于导电性弛豫(ECR)测量的非线性曲线拟合程序估计。但是,限制机制(或K和D的可用性)和实验缺陷(如气态组成变化,τF)的实验缺陷(如冲洗延迟)在时域ECR数据中并不明确地反映,以及K和K的准确性d要求对拟合误差进行仔细的敏感性分析。这里,提出了从时域ECR数据转换的特征时间(DCT)的分布,以克服上述挑战。据证明,从DCT频谱,易于识别速率限制机制和τf的效果,并且可以结合k,d和τf的值。使用含有噪声的ECR数据验证K和D测定的强大稳健性。 DCT光谱开辟了一种可见和可信地确定MiEC陶瓷氧化物的动力学参数的方法。

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