A Comparative Study of Equivalent Circuit Models for Electro-Chemical Impedance Spectroscopy Analysis of Proton Exchange Membrane Fuel Cells

Electrochemical impedance spectroscopy is one of the important tools for the performance analysis and diagnosis of proton exchange membrane fuel cells. The equivalent circuit model is an effective method for electrochemical impedance spectroscopy resolution. In this paper, four typical equivalent circuit models are selected to comprehensively compare and analyze the difference in the fitting results of the models for the electrochemical impedance spectroscopy under different working conditions (inlet pressure, stoichiometry, and humidity) from the perspective of the fitting accuracy, change trend of the model parameters, and the goodness of fit. The results show that the fitting accuracy of the model with the Warburg element is the best for all under each working condition. When considering the goodness of fit, the model with constant phase components is the best choice for fitting electrochemical impedance spectroscopy under different inlet pressure and air stoichiometry. However, under different air humidity, the model with the Warburg element is best. This work can help to promote the development of internal state analysis, estimation, and diagnosis of the fuel cell based on the equivalent circuit modeling of electrochemical impedance spectroscopy.

Battery State Estimation with ANN and SVR Evaluating Electrochemical Impedance Spectra Generalizing DC Currents

The demand for energy storage is increasing massively due to the electrification of transport and the expansion of renewable energies. Current battery technologies cannot satisfy this growing demand as they are difficult to recycle, as the necessary raw materials are mined under precarious conditions, and as the energy density is insufficient. Metal–air batteries offer a high energy density as there is only one active mass inside the cell and the cathodic reaction uses the ambient air. Various metals can be used, but zinc is very promising due to its disposability and non-toxic behavior, and as operation as a secondary cell is possible. Typical characteristics of zinc–air batteries are flat charge and discharge curves. On the one hand, this is an advantage for the subsequent power electronics, which can be optimized for smaller and constant voltage ranges. On the other hand, the state determination of the system becomes more complex, as the voltage level is not sufficient to determine the state of the battery. In this context, electrochemical impedance spectroscopy is a promising candidate as the resulting impedance spectra depend on the state of charge, working point, state of aging, and temperature. Previous approaches require a fixed operating state of the cell while impedance measurements are being performed. In this publication, electrochemical impedance spectroscopy is therefore combined with various machine learning techniques to also determine successfully the state of charge during charging of the cell at non-fixed charging currents.

Potentiodynamic Electrochemical Impedance Spectroscopy of Polyaniline-Modified Pencil Graphite Electrodes for Selective Detection of Biochemical Trace Elements

In this study, we analyzed the application of potentiodynamic electrochemical impedance spectroscopy (PDEIS) for a selective in situ recognition of biological trace elements, i.e., Cr (III), Cu (II), and Fe (III). The electrochemical sensor was developed using the electropolymerization of aniline (Ani) on the surface of the homemade pencil graphite electrodes (PGE) using cyclic voltammetry (CV). The film was overoxidized to diminish the background current. A wide range of potential (V = −0.2 V to 1.0 V) was investigated to study the impedimetric and capacitive behaviour of the PAni/modified PGE. The impedance behaviors of the films were recorded at optimum potentials through electrochemical impedance spectroscopy (EIS) and scrutinized by means of an appropriate equivalent circuit at different voltages and at their corresponding oxidative potentials. The values of the equivalent circuit were used to identify features (charge transfer-resistant and double layer capacitance) that can selectivity distinguish different trace elements with the concentration of 10 μM. The PDEIS spectra represented the highest electron transfer for Cu (II) and Cr (III) in a broad potential range between +0.1 and +0.4 V while the potential V = +0.2 V showed the lowest charge transfer resistance for Fe (III). The results of this paper showed the capability of PDEIS as a complementary tool for conventional CV and EIS measurement for metallic ion sensing.

Adsorption Free Energy of Glycine on TiO2 in Water from First Principles Simulations and Electrochemical Impedance Spectroscopy

The adhesion of amino acids and small organic molecules on TiO2 nanoparticles is fundamental for bio-nano functionalization of peptides and proteins. The adsorption free energy is the main physical quantity that regulates the adsorption process. Its evaluation is particularly challenging both experimentally, due to the weak interfacial signal in aqueous environments, and by atomistic simulations, due to the complexity of the physical phenomena occurring at the solid-water interface (polarization and charge transfer effects). We report here an accurate experimental-computational study of hydrated TiO2 nanoparticles interacting with Glycine where we obtain quantitative agreement of the measured adsorption free energy. Ab-initio simulations are performed within the Tight Binding Density Functional Theory in combination with enhanced free energy sampling techniques. The experiments adopt a new and efficient set-up for electrochemical impedance spectroscopy measurements based on screen-printed gold electrodes. The measured adsorption free energy is about -30 kJ/mol (both from experiment and calculation), with preferential interaction of the charged NH3 group which strongly adsorbs on the TiO2 bridging oxygens. The perfect agreement between computation and experiment opens the doors to an extended exploration of the bio-nano interaction for different materials and molecules.