Galvanodynamic Electrochemical Impedance Spectroscopy on a Solid Oxide Cell Stack for In-Operando Diagnostics

Abstract

Introduction Lifetime expectations and uncertainties regarding end-of-life performance hinder widespread deployment of fuel cell technology. Conventional cell performance diagnostic methodologies rely upon either ex-situ measurements, which lack an immediate connection with the physical degradation phenomena, or upon single cell in-operando electrochemical impedance spectroscopy (EIS), which often is troubled by challenges of feature identification of the spectra and uncomplete representation of the full stack operating conditions in large scale systems [1]. To address these problems, we propose to use electrochemical impedance spectroscopy techniques as diagnostic and prognostic tools to predict the cause-effect relationship between degradation phenomena and stack operating conditions. This experimental methodology can be potentially integrated into commercial systems for stack state of health monitoring during continuous operation. Experimental methods Through experimental study on a solid oxide fuel cell (SOFC) short stack, we explore the potential use of electrochemical impedance spectroscopy (EIS) for in-operando diagnosis. We identify the mechanisms contributing to this system EIS, by carrying out pristine cell/stack tests at different operating conditions (gas partial pressure, current, temperature).We collect experimental data on a 6-cell short-stack with active area of 80 cm2 per cell. Each anode-supported cell features a Ni-YSZ fuel electrode (240 μm), a Sr-doped LaMnO3 (LSM) oxygen electrode (40 μm) and an 8 mol% Y2O3 stabilized Zirconia (YSZ) electrolyte (8 μm). In our experimental setup, the first (reference electrode, i.e., cathode of cell no.1) and last (i.e., anode of cell no.6) electrodes are connected to the counter and working electrode leads of the potentiostat, respectively. This allows connecting the diagnostic system in parallel with the load and the stack, while performing floating ground galvanodynamic EIS measurements. This configuration enables the load to impose the operating current of the stack, while the potentiostat modulates the signal without any current in its main circuit. Reference and working sensing connections to individual cells in the stack are independent on the potentiostat leads.We operate the stack with mixtures of hydrogen, nitrogen and steam at the fuel electrode and mixtures of oxygen and nitrogen/helium at the oxygen electrode. We control the operating temperature via an electric furnace, while monitoring the stack temperatures with a set of six thermocouples, as reported in [2]. Discussion Figure 1 compares the measured EIS spectra for each cell in the short stack at beginning of life and after a major degrading event. With continuous stack monitoring, we are able to identify how degradation phenomena differently impact the state of health of the cells during the stack normal operation. This allows identifying the most degrading operating conditions of the system in real-time, hence informing the operational planning and lifetime maximization strategies of the system. Conclusions Preliminary results suggest that our methodology can provide meaningful insights regarding the cause and nature of the physical processes at the origin of degradation phenomena in solid oxide cells. This process is particularly interesting as a non-disruptive diagnostic and prognostic tool for commercial scale systems that need to optimize their operating conditions to either maximize their lifetime or meet a performance target at end-of-life.Figure 1 – (left) Beginning of life and (right) degraded cell plot comparison of experimental EIS for a 6-cell short stack at 1 A. Tstack=750°C, Anode flow=1.2 Nl min-1 (N2/H2=50/50%), Cathode flow=18.9 Nl min-1 (Air)[1] A. Baldinelli, L. Barelli, G. Bidini, A. Di Cicco, R. Gunnella, M. Minicucci, A. Trapananti, 2019, p. 020012.[2] L. Mastropasqua, S. Campanari, J. Brouwer, J. Power Sources 2017, 371, 225–237. Figure 1