Characterization of a Nickel / Gadolinia Doped Ceria Fuel Electrode for Co-Electrolysis
Authors: Esau Daniel , Grosselindemann Cedric , Sckuhr Soeren Peter , Kullmann Felix , Wissmeier Lena , Weber Andre 
Published: September 2023

Modelling of the high temperature co-electrolysis process requires understanding of the underlying reaction pathways. These include the electrochemical steam reduction, the electrochemical CO2 reduction and their coupling via the catalytic (reverse-)water-gas-shift reaction (RWGS). The assumption of a very fast water-gas-shift reaction and therefore neglectable CO electro-oxidation is widely used. The validity of this assumption has been previously investigated and proven to be sufficient by Kromp et al. [1] for an anode supported cell (ASC) with a nickel / yttria-stabilized zirconia (Ni/YSZ) fuel electrode.
Within this contribution we aim to extend the approach by Kromp et al. [1] towards an electrolyte-supported cell (ESC) with a nickel / gadolinium-doped ceria (Ni/CGO) fuel electrode. Previously, it has been proposed, that the electro-oxidation /-reduction of CO / CO2 can be present under reformate gas mixtures [2,3] on Ni/CGO fuel electrodes. However, a detailed comparison of pure activation resistance contributions during different operating modes has not been performed yet.
We present results from a complex variation of operating parameters (such as various gas compositions, exemplarily shown in fig. 1) for process identification by the use of electrochemical impedance spectroscopy and the subsequent impedance analysis by the distribution of relaxation times (DRT). Visualization and deconvolution of gas diffusion impedance contributions is done via the evaluation of the polarization resistance differences with different inert gases. This has been successfully applied for binary gas mixtures of hydrogen and steam [4] and also CO2 and CO. [5] The applicability of this method towards more complex multicomponent gas mixtures incorporating hydrogen, steam, CO2 and CO will be shown. By subtracting the gas diffusion impedance contributions, it is possible to evaluate reaction kinetics of the underlying activation polarization and a meaningful comparison of operation modes is facilitated. The ratio of direct CO2electro-reduction and CO2-conversion by RWGS will be discussed for different compositions and temperatures to show a non-neglectable influence of the CO2 electroreduction at even lower pCO2 / pH2 ratios than previously reported. Furthermore, we compare our results with ones obtained from Ni/YSZ fuel electrodes, to investigate the influence of fuel electrode structure and material.

References:

[1] A. Kromp et al., J. Electrochem. Soc., 158 (8) B980-B986 (2011).
[2] M. Riegraf et al., ACS Catal.
7
, 7760-7771 (2017).
[3] E. Ioannidou et al., J.Catal.
404, 174-186 (2021).
[4] C. Grosselindemann et al., J. Electrochem. Soc., 168, 124506 (2021).
[5] C. Grosselindemann et al., Proceedings of the 15th EFCF, July 5th-8th (2022).
Figure 1: Electrochemical impedance spectra recorded at open circuit and T = 860 °C of a symmetrical Ni/CGO fuel electrode under atmospheres of H2, H2O, CO and CO2 with varying CO/CO2-content. Gas mixtures have been applied in equilibrium compositions determined by the (reverse-)water-gas-shift reaction.

Figure 1