A Dynamic Multi-Scale Model for Solid Oxide Cells Validated on Local Current Measurements: Impact of Global Cell Operation on the Electrodes Reaction Mechanisms

Abstract

A dynamic physically based model has been developed to unravel the complex relationships between the overall Solid Oxide Cells (SOCs) response and the reaction mechanisms taking place in the electrodes. This numerical tool combines modules for different length-scales from the electrode microstructure up to the single repeat unit. First, models have been developed to emulate digital twins of electrode microstructures made of the classical SOCs materials [1]. The microstructural properties of the active layers and the current collectors are then computed on the synthetic volumes and used as inputs in the electrochemical models. The microscale models for the active layers take into account the mass and the charge transport phenomena for the solid and gas phases. For each electrode, the proposed reaction mechanism is split in a sequence of elementary steps with different pathways that can be activated depending on the polarization [2, 3]. The electrode models are finally coupled with a macroscopic description including the cell geometry and the design of the gas channels [4]. This model allows computing the cell polarization curves, the overpotentials and the EIS together with the distribution of the local current density and gas composition in the single repeat unit. This multiscale model has been used to study a typical cell made of the classical SOCs materials: the electrolyte was in Yttria Stabilized Zirconia (YSZ) whereas the hydrogen and oxygen electrodes were respectively composed by a cermet of Nickel and YSZ (Ni-YSZ) and a composite of Lanthanum doped Strontium Cobaltite Ferrite and Ceria doped Gadolinium Oxide (LSCF-CGO). For this cell, the representativeness of the electrodes synthetic microstructures have been checked on reconstructions obtained by tomographic techniques. It has been shown that the synthetic electrodes reproduce accurately the real microstructures. Moreover, the models at the electrode level have been carefully validated on polarizations curves and Electrochemical Impedance Spectra (EIS) measured on symmetrical cells using a three-electrode setup. It is worth noting that the electrodes of the tested symmetrical cells were manufactured using the same materials and composition than the complete cell. Finally, a specific attention has been paid in this work to validate the approach with an original experimental setup allowing the measurement of the local current densities on the full cell without electrode segmentation. This setup is composed of nine symmetrical-spaced pins that perform the measurement of local polarization curves from the inlet to the cell outlet. A campaign of tests has been carried out in fuel cell and electrolysis mode with different temperatures and flow rates. A good agreement has been found between the experimental and simulated data. It has been shown that the model is able to reproduce the evolution of the local polarization curves with a higher current density at the cell inlet. Furthermore, the simulated EIS for the cell have been found to be consistent with the experimental ones. The fully validated model has been used to analyze the cell operation in electrolysis and fuel cell mode. The reaction pathways associated to the elementary steps in the active layers have been discussed depending on the position within the electrodes and the polarizations. This model will then be used to implement the degradation laws such as the Ni agglomeration and compute the loss of cell performances and the remaining useful lifetime [5]. Moreover, the model could be applied to interpret the evolution of the EIS upon operation. [1] H. Moussaoui, J. Laurencin, Y. Gavet, G. Delette, M. Hubert, P. Cloetens, T. Le Bihan, J. Debayle, Stochastic geometrical modeling of solid oxide cells electrodes validated on 3D reconstructions, Computational Materials Science. 143 (2018) 262-276. [2] F. Monaco, E. Effori, M. Hubert, E. Siebert, G. Geneste, B. Morel, E. Djurado, D. Montinaro, J. Laurencin, Electrode Kinetics of Porous Ni-3YSZ Cermet Operated in Fuel Cell and Electrolysis Modes for Solid Oxide Cell Application. Under review. [3] E. Effori, J. Laurencin, E. Da Rosa Silva, M. Hubert, T. David, M. Petitjean, L. Dessemond, E. Siebert, An elementary kinetic model for the LSCF and LSCF-CGO electrodes for solid oxide cells: impact of oxygen partial pressure and degradation on the electrode response. Under review. [4] J. Laurencin, D. Kane, G. Delette, J. Deseure, F. Lefebvre-Joud, Modelling of solid oxide steam electrolyser: Impact of the operating conditions on hydrogen production. Journal of Power Sources. 196 (2011) 2080-2093. [5] M. Hubert, J. Laurencin, P. Cloetens, B. Morel, D. Montinaro, F. Lefebvre-Joud, Impact of Nickel agglomeration on Solid Oxide Cell operated in fuel cell and electrolysis modes. Journal of Power Sources. 397 (2018) 240-251. Figure 1