CO2 capture and sequestration (CCS) from stationary flue gas sources is one of the critical technologies needed as the future energy landscape shifts to low carbon intensity energy systems. Molten carbonate fuel cells (MCFCs) have the potential to capture CO2 from flue gas at higher thermal efficiency than traditional CCS technologies while simultaneously producing electricity. Herein, we present an investigation of molten carbonate fuel cell behavior at carbon capture conditions using simulated natural gas combined cycle flue gas. Measurements at these low CO2 and high current conditions reveal a lower than expected cathodic consumption of CO2 Based on the strong dependence of this deviation on water partial pressure as well as mass balances revealing a net consumption of water at the cathode, a parallel oxygen reduction mechanism is proposed. In this mechanism, water and oxygen are consumed at the cathode to produce hydroxide ions which migrate through the electrolyte to the anode. This parallel mechanism contributes to power generation but not to CO2 capture. Mass transport limitations in the molten carbonate fuel cell cathode were identified as the primary driver for this alternative mechanism which were heavily influenced by the design of the current collector and cathode interface.

Molten Carbonate Fuel Cells (MCFCs) are commercially employed in MW-scale power production, and recently are being developed also for carbon capture. Past experiments showed that MCFC performance with wet cathode feeding was higher than with dry cathode feeds at otherwise similar conditions. This was ascribed to a mechanism that predicted the water increasing the apparent CO 2 diffusion rate. However, recent tests performed at low CO 2 cathode feed concentrations, as in carbon capture service, showed the emergence of a different water effect. Namely, there seems to be an electrochemical reaction path attributable to water, involving hydroxide ions that runs parallel with the main path involving CO 2 . This results in lower CO 2 transfer from the cathode to the anode than what can be calculated from the electrical current. For the first time, here, a theoretical analysis will be presented to introduce a kinetic expression for MCFCs working under this dual-ion regime. Focus will be given to the expression of CO 2 and water polarization to assess the ratio between the current due to the two anions. Simulation and experimental results will be discussed providing a reliable and effective basis for the performance optimization of the MCFCs both in power and in carbon capture applications.

Conventional electrochemical characterization techniques based on voltage and current measurements only probe faradaic and capacitive rates in aggregate. In this work we develop a scanning thermo-ionic microscopy (STIM) to probe local electrochemistry at the nanoscale, based on imaging of Vegard strain induced by thermal oscillation. It is demonstrated from both theoretical analysis and experimental validation that the second harmonic response of thermally induced cantilever vibration, associated with thermal expansion, is present in all solids, whereas the fourth harmonic response, caused by local transport of mobile species, is only present in ionic materials. The origin of STIM response is further confirmed by its reduced amplitude with respect to increased contact force, due to the coupling of stress to concentration of ionic species and/or electronic defects. The technique has been applied to probe Sm-doped Ceria and LiFePO 4 , both of which exhibit higher concentrations of mobile species near grain boundaries. The STIM gives us a powerful method to study local electrochemistry with high sensitivity and spatial resolution for a wide range of ionic systems, as well as ability to map local thermomechanical response.

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Molten Carbonate Fuel Cells (MCFCs) are used in MW-scale power plants. Recently, they have also been explored for carbon capture. A recent MCFC experimental campaign for carbon capture applications has shown interesting results. It revealed that at carbon capture conditions a secondary reaction mechanism involving hydroxide ions starts to affect cell performance. This is important since part of the electricity produced will be used to transfer water instead of CO 2 , decreasing capture efficiency. Previously, the authors developed a dual-ion model for MCFCs to account for the observed loss of carbon capture efficiency at low-CO 2 cathode gas conditions. A more recent, deeper exploration of MCFC control parameters found that the split between the competing reaction paths depends not only on the cathode gas composition, but also on cathode diffusion resistance. Thus, in this work we increase the applicability range and reliability of the dual-ion electrochemical model by including the diffusion of reactants in the porous cathode along the axis perpendicular to the cell plane. This transport component can account for the shifting of carbonate and hydroxide contributions to the overall cell current as a function of cathode feed properties and for different current collector designs that determine the diffusion resistance term.