Enhancement of redox cycling stability of Ni/GDC cermets for intermediate-temperature SOFC anodes through Ge incorporation in the ceramic phase

Abstract

In this study, Ge4+ was incorporated into the ceramic matrix of nickel-based anode materials, synthesizing anode materials NiO-Gd0.1Ce0.9-xGexO1.95 (x = 0.01, 0.04, 0.07) and NiO-Ce0.9Gd0.1O2–δ. Corresponding anode support samples were also prepared, designated as A-CGDC, A-C1Ge, A-C4Ge, and A-C7Ge. Additionally, single cell samples using the newly co-doped anode materials were prepared, identified as C-CGDC, C-C1Ge, C-C4Ge, and C-C7Ge. The research indicates that after doping the ceramic phase framework with Ge4+, these composite anode materials exhibit the potential to withstand more redox cycles than C-CGDC without catastrophic mechanical structural damage or degradation in electrochemical performance. Particularly, after incorporating 7mol% Ge4+ into the ceramic backbone, the issue of 86 % strain accumulation in the anode support was mitigated. Additionally, the ion doping ratio is closely linked to the stability of the single cell samples, with the A-C7Ge sample able to withstand up to 11 extreme recycling sessions at 700 °C without complete structural failure, improving structural stability by approximately 57 % compared to A-C1Ge. In terms of electrochemical output performance, the impedance of C-C1Ge prior to complete failure was nearly double that before oxidation-reduction, with a maximum power density reduction of about 26.47 %. As the co-doping concentration in the ceramic phase reached 7mol%, the impedance increase during single cell cycle testing was about four times smaller, with C-C7Ge 's impedance before mechanical failure only 37 % higher than before cycling, and a reduction in maximum power density of just 11.11 %. Moreover, during consecutive cycling tests, the average damage to the open-circuit voltage was only 0.02V, showing almost no negative impact from the cycling operations, and it maintained efficient output performance after multiple cycles. Therefore, the newly synthesized nickel-based anode materials, modified via co-doping methods within the ceramic phase, can be considered as potential composite anode materials for intermediate-temperature solid oxide fuel cells.