Novel Composite Fuel Electrode for CH4-SOFC and CO2-SOEC
Authors: Duranti Leonardo , Luisetto Igor , D'Ottavi Cadia , Di Bartolomeo Elisabetta 
Published: July 2021

Reversible solid oxide cells (RSOCs) represent a promising technology for the efficient exploitation of intrinsically intermittent renewable energy sources. RSOCs allow to derive fuel and chemicals from power (power-to-gas technology, P2G) and power from fuel and chemicals (gas-to-power technology, GTP) and can be interchangeably operated either as a solid oxide fuel cell (SOFC) or as a solid oxide electrolyzer cell (SOEC). The key aspect to render these devices competitive on a market scale is the development of multi-tasking, reliable, cost-effective and long-lasting electrodes (1,2). Besides, to overcome the issues related to hydrogen production, storage and distribution (e.g. impractical conversion of the existing grid to hydrogen-based infrastructures), the fuel-electrode of RSOCs should ensure high catalytic activity and coking resistance toward carbon-containing species (3-4). Using a hydrocarbon-tolerant fuel electrode, energy can be obtained by natural gas and biogas (SOFC-mode), with useful recovery of CO2 in the exhausts (carbon capture and storage, CCS). Besides, if the electrode is also active towards CO2 electrolysis (SOEC mode), CO2 is reduced to CO and O2 (carbon capture and utilization, CCU).

Ni-YSZ is the reference fuel-electrode material for both H2 fed SOFC and for CO2 electrolysis in SOEC. Nevertheless, Ni-based cermets cannot be used in SOFCs fed with methane-containing fuels, as they suffer from two main drawbacks: mechanical instability upon NiO-Ni redox cycles (5) and passivation due to coking, being Ni a catalyst for methane cracking (3, 4). Moreover, during Ni-YSZ operation in CO2-SOEC mode, ZrO2 reduction can occur at high cathodic potential, resulting in Ni-Zr compounds formation (6).

In this work, a recently developed (7, 8) composite material containing La0.6Sr0.4Fe0.8Mn0.2O3-δ (LSFMn) and 5wt% Ni-containing Ce0.58Sm0.15O2-δ (NiSDC) is tested as fuel electrode for LSGM-electrolyte supported cells. In reducing conditions, Fe exsolved from the LSFMn perovskite forms a Fe-Ni alloy with Ni present on SDC. In SOFC mode, the composite is designed to operate in dry methane: Fe-Ni catalytic sites activate CH4, which is successively oxidized on Mn-containing LSFMn, while SDC increases the O2- supply at the anode to get rid of any carbonaceous deposits. As Fe-Ni alloy was reported to be highly active for CO2 reduction (9), the composite was also tested as SOEC cathode in different CO2:CO ratios. LSFMn+NiSDC was tested in SOFC-mode as anode for hydrogen, dry methane and carbon monoxide oxidation and showed power density outputs of 657, 668 and 527 mW/cm2, respectively (Fig. a), a redox stable behavior and coking resistance for over 120 h. LSFMn+NiSDC in SOEC-mode delivered 2.66 A/cm2 at 2 V in 95:5 CO2:CO mixture (Fig. b), keeping 1 A/cm2 of current density output for over 40 h.

(1) - M. Mogensen, M. Chen, H. Frandsen, C. Graves, J. Hansen, K. Hansen, A. Hauch, T. Jacobsen, S. Jensen, T. Skafte, Reversible solid-oxide cells for clean and sustainable energy, Clean Energy, 3 (2019) 175-201.

(2) - M.B. Mogensen, Materials for Reversible Solid Oxide Cells, Current Opinion in Electrochemistry, (2020).

(3) - M. Mogensen, K. Kammer, Conversion of hydrocarbons in solid oxide fuel cells, Annual Review of Materials Research, 33 (2003) 321-331.

(4) - S. McIntosh, R.J. Gorte, Direct hydrocarbon solid oxide fuel cells, Chemical reviews, 104 (2004) 4845-4866.

(5) - J. Malzbender, R. Steinbrech, Advanced measurement techniques to characterize thermo-mechanical aspects of solid oxide fuel cells, Journal of Power Sources, 173 (2007) 60-67

(6) - A. Hauch, K. Brodersen, M. Chen, M.B. Mogensen, Ni/YSZ electrodes structures optimized for increased electrolysis performance and durability, Solid State Ionics, 293 (2016) 27-36

(7) - L. Duranti, I. Luisetto, S. Licoccia, C. Del Gaudio, E. Di Bartolomeo, Electrochemical performance and stability of LSFMn+ NiSDC anode in dry methane, Electrochimica Acta, (2020) 137116.

(8) - L. Duranti, I.N. Sora, F. Zurlo, I. Luisetto, S. Licoccia, E. Di Bartolomeo, The role of manganese substitution on the redox behavior of La0.6Sr0.4Fe0.8Mn0.2O3-δ, Journal of the European Ceramic Society, (2020)

(
9
) - Liu, S., Liu, Q., & Luo, J. L. (2016). Highly stable and efficient catalyst with in situ exsolved Fe–Ni alloy nanospheres socketed on an oxygen deficient perovskite for direct CO2 electrolysis. ACS Catalysis, 6(9), 6219-6228.

Figure 1