Perovskite chromite-based fuel electrode for solid oxide cells (SOCs): towards the understanding of the electrochemical performance

Kurzfassung

The current energy transition is a key driver for the continuous development of fuel cells and electrolyzers due to the rapid growth of the clean energy demand and the need to overcome the intermittency of the power supply of renewable energy sources, such as wind and solar energy. In this regard, solid oxide cells (SOC) are promising systems that allow to overcome such fluctuations: they convert renewable electrical energy into chemical energy in the form of hydrogen and valuable fuels and chemicals, while they can also repower the grid by converting fuels and hydrogen into electrical power. This feature in reversibility has attracted the interest among Power-to-X technologies, which can be exploited by operating SOCs in fuel cell (SOFC), electrolysis (SOEL) and reversible (rSOC) modes. Nevertheless, SOCs are not yet a mature technology due to limitations on the performance of their electrolyte and electrodes. Typical fuel electrodes made of Ni-based cermets are in contact not only with hydrogen, but also with reactants such as natural gas, biogas, steam and carbon dioxide, leading to important operation issues related to high temperatures and poisoning tolerance, which significantly detriment the performance of these systems. Due to the urgent need for the development of sustainable SOC systems in clean energy scenarios, this thesis aims to cover the Ni cermets issues related to SOCs operation, such as nickel agglomeration, nickel migration, structural cell damage and carbon deposition. Therefore, with the motivation to propose alternative fuel electrode materials to the state-of-the-art Ni cermets, formulations of perovskite chromite-based fuel electrodes were investigated in different SOC operating conditions. Firstly, different perovskite compositions were investigated by X-ray diffraction (XRD) to ensure the desired phase. With these crystal structure characterizations, the lanthanum-chromite perovskite with Ni doping (LSCrN) was selected as candidate fuel electrode material with the compositions La0.7Sr0.3Cr0.85Ni0.15O3-δ (L70SCrN) and La0.65Sr0.3Cr0.85Ni0.15O3-δ (L65SCrN). These materials were synthetized by the glycine-nitrate combustion method and ceramic powder morphology was characterized by scanning electron microscopy (SEM). An experimental protocol for the cell manufacturing process was designed and the electrolyte-supported-cells (ESCs) were produced by screen-printing, drying and sintering processes. ESCs were tested in different operating SOC modes: fuel cell (SOFC), steam electrolysis (SOEL), steam and carbon dioxide co-electrolysis (co-SOEL), as well as in reversible mode (rSOC) and even in dry carbon dioxide electrolysis operation. In situ electrochemical characterizations were performed by evaluating the voltage - current response and the electrochemical impedance spectroscopy (EIS). In parallel, the exsolution of nickel particles from the produced LSCrN ceramic powders was investigated by means of temperature programmed reduction (TPR), X-ray spectroscopy (XPS) and XRD techniques. It was shown that the introduction of A-site deficiency promoted the reduction of metallic nickel particles on the perovskite surface. The particle distribution was found to be dependent on the temperature, the atmosphere and the overpotential. In co-SOEL operation, cells with the developed L65SCrN electrode showed a comparable performance to the ones with state-of-the-art Ni cermets, e.g. - 0.8 A·cm-2 at 1.32 V and 860 °C. The long-term stability (~ 1000 hours) suggested that under strongly reducing atmospheres, such as in SOEL at 860 °C, the L65SCrN electrode suffered from accelerated performance degradation due to an alteration of the transport properties. Nonetheless, it was found that a decrease in operating temperature (below 830 °C) could be a suitable strategy to mitigate this durability issue. These findings are related to a gain in performance of the perovskite electrodes against the state-of-the-art Ni electrodes at temperatures between 770 °C and 830 °C, possibly due to lower reaction energy barriers. These outcomes were used as basis for a scale-up analysis from the cell level up to the system level, i.e. up to the MW scale, by analyzing a real case application of SOEL-based systems for hydrogen production. This analysis suggested that the implementation of perovskite electrodes in SOEL systems, together with a decrease of the system operating temperature, would lead to a significant reduction of the number of cells in the stacks and hence of the system components, simplifying the system layout. Additionally, the required amount of Ni raw material would also be significantly decreased, which would mitigate future supply chain issues that the mineral market may experience in the upcoming years. This study paves the way for future alternative electrode development for SOC applications while suggesting potential benefits at the system scale.