Reversible Metal Supported Solid Oxide Cells
Authors: Hagen Anke , Tasca Davide , De-Faria Agathe , Capotondo Federico , Caldogno Riccardo , Sudireddy Bhaskar Reddy , Sun Xiufu 
Published: September 2023

Solid oxide fuel cells (SOFCs) excel by high efficiencies in fuel cell as well as electrolysis modes, and by being able to operate in both modes as a reversible cell (solid oxide cell – SOC). This allows for production of electricity and heat from a green fuel, and for storage of electricity as gas or use as fuel. Lifetime and costs are major factors enabling such reversible SOCs to enter green energy systems. Metal supported SOCs (MSCs) provide cost-competitive materials within the cell. Furthermore, targeting the lower operating temperatures around 650 oC, MSCs will allow for cheaper stack and balance of plant components as well. Lowering operating temperatures leads to a reduction of thermally activated degradation processes, thereby prolonging the lifetime. The present study investigates the option to operate MSCs, fabricated at DTU Energy by tape casting, lamination, and screen-printing, in reversible mode between fuel cell (FC) and electrolysis (EC). Emphasis is on the effect of reversible operation on performance and durability of the MSC, compared to steady state operation in either mode, and to the behavior of state-of-the-art (SoA) fuel electrode supported SOC with Ni/YSZ fuel electrode. The MSCs are composed of a FeCr support, a Ni/GDC (gadolinium-doped ceria) infiltrated LSFNT (lanthanum-doped strontium iron nickel titanate) fuel electrode, a YSZ (yttria-stabilized zirconia) electrolyte, a GDC barrier layer, and an in situ sintered LSC (lanthanum-doped strontium cobaltite) air electrode. The reversible operation was carried out by switching between FC and EC modes at current densities of 0.25 and -0.25 A/cm2, respectively, at 650 oC using a gas mixture of 50/50 H2O/H2 to the fuel electrode and air to the oxygen electrode.
Figure 1 shows the evolution of the cell voltages for the SoA cell and the MSC. The degradation rate of the SoA cell was larger during operation in EC as compared to FC mode. Similar observations were made previously, even though these tests were typically carried out at temperatures higher than 650 oC as in this work [1]. Furthermore, the degradation rate decreases over time, more particularly in EC mode, which is also a known phenomenon at this type of cells [2, 3]. In the final ca. 200 h, both degradation rates are in the range of 3%/1000 h, which is an interesting observation, i.e., the longer-term degradation rates are similar in both modes (EC and FC). The analysis of electrochemical impedance spectroscopy (EIS) recorded under current allowed to conclude that the main contribution to the degradation is the increase of polarization resistance, i.e., related to electrodes degradation.
In the initial ca. 400 h hundred hours, the cell voltage degradation on the MSC is larger in fuel cell mode, while there is nearly no degradation in electrolysis mode. The good stability in EC mode over a few hundred hours confirms the findings of steady-state electrolysis tests with the same type of cells [4]. In the final period from ca. 600 h, both degradation rates increase but stay fairly constant with ca. 4%/1000 h in EC and ca. 16%/1000 h in FC mode, when calculated as linear increase. EIS reveals that both, the serial and the polarization resistances increase in parallel, which indicates a combination of degradation of electrode and probably corrosion and/or interface attachment. Details will be presented, including comprehensive EIS evaluation combined with micro-structural characterization.
Figure 1. Cell voltage vs. operating time under current in reversible mode at 650 oC, 0.25 A/cm2 in fuel cell and -0.25 A/cm2 in electrolysis mode, 50/50 H2O/H2 fuel and air to the oxygen electrode, (a) SoA cell, (b) MSC, gaps in the cell voltage are interruptions of operation due to technical issues in the lab
References
[1] X. Sun, B.R. Sudireddy, X. Tong, M. Chen, K. Brodersen, A. Hauch, Optimization and Durability of Reversible Solid Oxide Cells, ECS Trans. 91 (2019) 2631.
[2] A. Hagen, R. Barfod, P.V. Hendriksen, Y.-L. Liu, S. Ramousse, Degradation of anode supported SOFCs as a function of temperature and current load, J. Electrochem. Soc. 153(6) (2006) A1165.
[3] A. Hauch, K. Brodersen, M. Chen, C. R. Graves, S. H. Jensen, P. S. Jørgensen, P. V. Hendriksen, M. B. Mogensen, S. Ovtar, X. Sun, A Decade of Solid Oxide Electrolysis Improvements at DTU Energy, ECS Transactions, 75(42) (2017) 3.
[4] A. Hagen, R. Caldogno, F. Capotondo, X. Sun, Metal Supported Electrolysis Cells, Energies 15 (2022) 2045.

Figure 1