单个伪电容纳米粒子中交换电流和离子扩散系数的浸渍测量法

Brian Roehrich,  and , Lior Sepunaru*, 
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引用次数: 0

摘要

在电分析技术中,电化学阻抗光谱(EIS)具有频率分辨率高的独特优势。这使得电化学阻抗能谱仪能够轻松地分解电化学装置的电容、电阻和扩散过程。在此,我们报告了对单个伪电容纳米粒子阻抗谱的测量结果。我们选择普鲁士蓝作为我们的模型系统,因为它将电子转移反应与钠离子插层--过程耦合在一起,虽然本质上是复杂的,但使用 EIS 可以很容易地解决。我们使用扫描电化学电池显微镜(SECCM)分离微滴中的单个普鲁士蓝颗粒,并使用多正弦快速傅立叶变换技术测量它们的阻抗谱。在此过程中,我们提取了每个粒子的交换电流密度和钠离子扩散率,它们分别说明了粒子的电子导电性和离子导电性。令人惊讶的是,这些参数在不同颗粒之间的差异超过一个数量级,而且与颗粒大小或相互之间没有关联。这种明显的异质性意味着,在一个假想的电池阴极中,一个活性粒子的电子传输速度可能比其相邻粒子快 10 倍;而另一个活性粒子则可能因钠离子传输迟缓而受到影响,与同一电极中其他地方性能更好的粒子相比,其充电速率能力受到限制。我们的研究结果揭示了这种内在异质性,同时证明了 EIS 在未来单颗粒研究中的实用性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Impedimetric Measurement of Exchange Currents and Ionic Diffusion Coefficients in Individual Pseudocapacitive Nanoparticles

Among electroanalytical techniques, electrochemical impedance spectroscopy (EIS) offers the unique advantage of a high degree of frequency resolution. This enables EIS to readily deconvolute between the capacitive, resistive, and diffusional processes that underlie electrochemical devices. Here, we report the measurement of impedance spectra of individual, pseudocapacitive nanoparticles. We chose Prussian blue as our model system, as it couples an electron-transfer reaction with sodium ion intercalation─processes which, while intrinsically convoluted, can be readily resolved using EIS. We used a scanning electrochemical cell microscope (SECCM) to isolate single Prussian blue particles in a microdroplet and measured their impedance spectra using the multi-sine, fast Fourier transform technique. In doing so, we were able to extract the exchange current density and sodium ion diffusivity for each particle, which respectively inform on their electronic and ionic conductivities. Surprisingly, these parameters vary by over an order of magnitude between particles and are not correlated to particle size nor to each other. The implication of this apparent heterogeneity is that in a hypothetical battery cathode, one active particle may transfer electrons 10 times faster than its neighbor; another may suffer from sluggish sodium ion transport and have restricted charging rate capabilities compared to a better-performing particle elsewhere in the same electrode. Our results inform on this intrinsic heterogeneity while demonstrating the utility of EIS in future single-particle studies.

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来源期刊
ACS Measurement Science Au
ACS Measurement Science Au 化学计量学-
CiteScore
5.20
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0.00%
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0
期刊介绍: ACS Measurement Science Au is an open access journal that publishes experimental computational or theoretical research in all areas of chemical measurement science. Short letters comprehensive articles reviews and perspectives are welcome on topics that report on any phase of analytical operations including sampling measurement and data analysis. This includes:Chemical Reactions and SelectivityChemometrics and Data ProcessingElectrochemistryElemental and Molecular CharacterizationImagingInstrumentationMass SpectrometryMicroscale and Nanoscale systemsOmics (Genomics Proteomics Metabonomics Metabolomics and Bioinformatics)Sensors and Sensing (Biosensors Chemical Sensors Gas Sensors Intracellular Sensors Single-Molecule Sensors Cell Chips Arrays Microfluidic Devices)SeparationsSpectroscopySurface analysisPapers dealing with established methods need to offer a significantly improved original application of the method.
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