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

Abstract

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.