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Electrochemical pressure impedance spectroscopy (EPIS) has received the attention of researchers as a method to study mass transport processes in polymer electrolyte mem-brane fuel cells (PEMFC). It is based on analyzing the cell voltage response to a harmonic excitation of the gas phase pressure in the frequency domain. Several experiments with a single-cell fuel cell have shown that the spectra contain information in the frequency range typical for mass transport processes and are sensitive to specific operating condi-tions and structural fuel cell parameters. To further benefit from the observed features, it is essential to identify why they occur, which to date has not yet been accomplished. The aim of the present work, therefore, is to identify causal links between internal processes and the corresponding EPIS features.
To this end, the study follows a model-based approach, which allows the analysis of inter-nal states that are not experimentally accessible. The PEMFC model is a pseudo-2D model, which connects the mass transport along the gas channel with the mass transport through the membrane electrode assembly. A modeling novelty is the consideration of the gas vol-ume inside the humidifier upstream the fuel cell inlet, which proves to be crucial for the reproduction of EPIS. The PEMFC model is parametrized to a 100 cm² single cell of the French project partner, who provided the experimental EPIS results reproduced and in-terpreted in the present study.
The simulated EPIS results show a good agreement with the experiments at current den-sities ≤ 0.4 A cm–2, where they allow a further analysis of the observed features. At the lowest excitation frequency of 1 mHz, the dynamic cell voltage response approaches the static pressure-voltage response. In the simulated frequency range between 1 mHz – 100 Hz, the cell voltage oscillation is found to strongly correlate with the partial pressure oscillation of oxygen, whereas the influence of the water pressure is limited to the low frequency region.
The two prominent EPIS features, namely the strong increase of the cell voltage oscillation and the increase of phase shift with frequency, can be traced back via the oxygen pressure to the oscillation of the inlet flow rate. The phenomenon of the oscillating inlet flow rate is a consequence of the pressure change of the gas phase inside the humidifier and in-creases with frequency. This important finding enables the interpretation of experimen-tally observed EPIS trends for a variation of operational and structural fuel cell parame-ters by tracing them back to the influence of the oscillating inlet flow rate.
The separate simulation of the time-dependent processes of the PEMFC model through model reduction shows their individual influence on EPIS. The sluggish process of the wa-ter uptake by the membrane is visible below 0.1 Hz, while the charge and discharge of the double layer becomes visible above 1 Hz. The gas transport through the gas diffusion layer is only visible above 100 Hz. The simulation of the gas transport through the gas channel
without consideration of the humidifier becomes visible above 1 Hz. With consideration of the humidifier the gas transport through the gas channel is visible throughout the fre-quency range. The strong similarity of the spectra considering the humidifier with the spectra of the full model setup shows the dominant influence of the humidifier on EPIS.
A promising observation is the change in the amplitude relationship between the cell volt-age and the oxygen partial pressure oscillation as a function of the oxygen concentration in the catalyst layer. At a frequency where the influence of oxygen pressure on the cell voltage is dominant, for example at 1 Hz, the amplitude of the cell voltage oscillation could be used to indirectly measure the oxygen concentration in the catalyst layer.
Electrochemical pressure impedance spectroscopy (EPIS) is an emerging tool for the diagnosis of polymer electrolyte membrane fuel cells (PEMFC). It is based on analyzing the frequency response of the cell voltage with respect to an excitation of the gas-phase pressure. Several experimental studies in the past decade have shown the complexity of EPIS signals, and so far there is no agreement on the interpretation of EPIS features. The present study contributes to shed light into the physicochemical origin of EPIS features, by using a combination of pseudo-two-dimensional modeling and analytical interpretation. Using static simulations, the contributions of cathode equilibrium potential, cathode overpotential, and membrane resistance on the quasi-static EPIS response are quantified. Using model reduction, the EPIS responses of individual dynamic processes are predicted and compared to the response of the full model. We show that the EPIS signal of the PEMFC studied here is dominated by the humidifier. The signal is further analyzed by using transfer functions between various internal cell states and the outlet pressure excitation. We show that the EPIS response of the humidifier is caused by an oscillating oxygen molar fraction due to an oscillating mass flow rate.
Electrochemical pressure impedance spectroscopy (EPIS) has recently been developed as a potential diagnosis tool for polymer electrolyte membrane fuel cells (PEMFC). It is based on analyzing the frequency response of the cell voltage with respect to an excitation of the gas-phase pressure. We present here a combined modeling and experimental study of EPIS. A pseudo-twodimensional PEMFC model was parameterized to a 100 cm2 laboratory cell installed in its test bench, and used to reproduce steady-state cell polarization and electrochemical impedance spectra (EIS). Pressure impedance spectra were obtained both in experiment and simulation by applying a harmonic pressure excitation at the cathode outlet. The model shows good agreement with experimental data for current densities ⩽ 0.4 A cm−2. Here it allows a further simulative analysis of observed EPIS features, including the magnitude and shape of spectra. Key findings include a strong influence of the humidifier gas volume on EPIS and a substantial increase in oxygen partial pressure oscillations towards the channel outlet at the resonance frequency. At current densities ⩾ 0.8 A cm−2 the experimental EIS and EPIS data cannot be fully reproduced. This deviation might be associated with the formation and transport of liquid water, which is not included in the model.
Mass transfer phenomena in membrane fuel cells are complex and diversified because of the presence of complex transport pathways including porous media of very different pore sizes and possible formation of liquid water. Electrochemical impedance spectroscopy, although allowing valuable information on ohmic phenomena, charge transfer and mass transfer phenomena, may nevertheless appear insufficient below 1 Hz. Use of another variable, that is, back pressure, as an excitation variable for electrochemical pressure impedance spectroscopy is shown here a promising tool for investigations and diagnosis of fuel cells.
Model-based analysis of Electrochemical Pressure Impedance Spectroscopy (EPIS) for PEM Fuel Cells
(2019)
Electrochemical impedance spectroscopy (EIS) is a widely-used diagnostic technique to characterize electrochemical processes. It is based on the dynamic analysis of two electrical observables, that is, current and voltage. Electrochemical cells with gaseous reactants or products, in particular fuel cells, offer an additional observable, that is, the gas pressure. The dynamic coupling of current or voltage with gas pressure gives rise to a number of additional impedance definitions, for which we have previously introduced the term electrochemical pressure impedance spectroscopy (EPIS) [1,2]. EPIS shows a particular sensitivity towards transport processes of gas-phase or dissolved species, in particular, diffusion coefficients and transport pathway lengths. It is as such complementary to standard EIS, which is mainly sensitive towards electrochemical processes. First EPIS experiments on PEM fuel cells have recently been shown [3].
We present a detailed modeling and simulation analysis of EPIS of a PEM fuel cell. We use a 1D+1D continuum model of a fuel/air channel pair with GDL and MEA. Backpressure is dynamically varied, and the resulting simulated oscillation in cell voltage is evaluated to yield the ▁Z_( V⁄p_ca ) EPIS signal. Results are obtained for different transport situations of the fuel cell, giving rise to very complex EPIS shapes in the Nyquist plot. This complexity shows the necessity of model-based interpretation of the complex EPIS shapes. Based on the simulation results, specific features in the EPIS spectra can be assigned to different transport domains (gas channel, GDL, membrane water transport).