Degradation behavior of Ni-YSZ anode-supported solid oxide fuel cell (SOFC) as a function of H2S concentration

This study investigated the effect of H₂S concentration (5, 10 and 50 ppm) on the degradation and performance of Ni-YSZ anode supported solid oxide fuel cells. When supplied with hydrogen fuel containing H₂S, the cell voltage dropped rapidly, and with increasing H₂S concentration, voltage drop % increased (due to higher sulfur coverage on the Ni surface) and saturated more rapidly. A high concentration (50 ppm) of H₂S led to an additional, slow rate voltage loss. In all cases, cell performance did not completely recover even after being supplied with H₂S-free hydrogen fuel, because of the incomplete desorption of sulfur from the Ni surface. After the performance tests, nickel sulfides were detected on the Ni surface by Raman spectra, which were produced by the reaction of the remaining adsorbed sulfur with Ni during the cooling process. This indicates that the formation of nickel sulfides was not responsible for the secondary voltage drop. SEM/EDS analyses combined with FIB revealed that the reason for the additional 2^nd drop was Ni oxidation; at a high sulfur coverage ratio (50 ppm), the outer layer of the Ni particle was oxidized by oxygen ions transported from the electrolyte. This indicates that H₂S concentration as well as current density is a critical factor for Ni oxidation, and gives rise to the second voltage drop (irreversible cell degradation). The present work showed that the degradation behavior and phenomenon can differ significantly depending on the concentration of H₂S, i.e., permanent changes may or may not occur on the anode (such as Ni oxidation) depending upon H₂S concentration.     

Computational analysis of atomic C and S adsorption on Ni,Cu, and Ni-Cu SOFC anode surfaces

Carbon deposition and sulfur poisoning are issues that limit the state-of-the-art Ni-YSZ anode material of solid oxide fuel cell to be used in direct hydro-carbon fuels. In the present study, density functional theory calculations are performed to investigate the adsorption of C and S on Ni(111), Cu(111) and alloyed Ni-Cu(111) surfaces. It is confirmed that C and S energetically favor the hollow sites of Ni(111) and Cu(111) surfaces; forming Ni-Cu alloy by addition of Cu into Ni weakens the adsorption of C and S with lowered adsorption energies due to less overlapping between the C 2p or S 3p and the metallic 3d orbits.     

Porous Ni/8YSZ anode of SOFC fabricated by the plasma sprayed method

In the present study, porous electrode coating of Ni/8YSZ on the interconnector material was made by the plasma-spraying. By introducing the pore former into the composite powder, the porous structure of SOFC anode will be obtained. By using the plasma spraying technique for SOFC fabrication, we can avoid the thermal failure between the components of SOFC which made from the traditional sintering method at high temperature. In this study, two kinds of composite powders in the granulate form were prepared, one with the nano carbon as a pore former and the other without the carbon. The results showed that the porous structure of SOFC anode could be achieved by the plasma spraying technique. The porosity of the anode made from the composite powder with pore former was 40%. Without pore former the porosity in the anode coating after hydrogen reduction was almost 30%. These results suggest that this method exhibits the potential to manufacture the porous ceramic/metal composite anode of SOFC to achieve the larger triple phase boundary for fuel oxidation.     

A theoretical study of sulfur poisoning tolerance at the interface of Mo doped Ni/Yttria-Stabilized Zirconia

Sulfur poisoning is a crucial problem for solid oxide fuel cell (SOFC) anode leading to increasing research works on the development of the anode materials with high sulfur tolerance. By the first principle calculations of hydrogen sulfide dissociation and sulfur atoms diffusion at the interface between the Ni or Mo-doped-nickel and Yttria-Stabilized Zirconia (YSZ), we find that Mo-doped-Ni/YSZ anode not only increases the hydrogen sulfide dissociation barriers, but also increases the barriers of the sulfur diffusion to the oxygen vacancy at the interface of Ni and YSZ, especially for YSZ in oxygen enriched conditions. Here we offer a new theoretical study of Mo-doped-Ni/YSZ sulfur poisoning tolerance at the interface.     

Experimental and thermodynamic evaluation of La1−xSrxMnO3±δ and La1−xSrxCo1−yFeyO3−δ cathodes in Cr-containing humidified air

Chemical and structural stability of strontium doped lanthanum manganite (LSM) and lanthanum cobalt ferrite (LSCF) cathodes in Cr-containing humidified air has been studied by a combination of experimental and thermodynamic approaches. During 100 h tests performed in flowing air (3% H₂O) at 1023 K, the electrochemical performance of LSM/yttria doped zirconia (YSZ)/Pt half-cells exhibited a relatively faster degradation in current (I–t) at 0.5 V applied bias than the LSCF/gadolinium-doped ceria (GDC)/Pt half-cells. Cr species from the gas phase deposited predominantly at LSM/YSZ interface while LSCF showed mainly surface deposition throughout the electrode. Raman spectra indicate SrCrO₄ formation on the post tested LSCF cathode but not on the post tested LSM cathode. The polarization resistance of the LSM cathode also increased significantly compared to that of the LSCF cathode. A linear programming approach coupled with first-principles thermodynamics suggests that the stoichiometric LSM remains stable and unreacted for the whole range of experimental P_CrO3 and temperature conditions whereas the formation of SrCrO₄ on LSC cathode is energetically favored at 1023 K supporting the experimental findings.     

Structural evolution of carbon deposition on a Ni/YSZ cermet of a SOFC analyzed by soft x-ray XANES spectroscopy

This paper investigated the structural evolution of carbon deposition on a Ni/YSZ cermet of a SOFC. The Ni/YSZ cermet was heated in CH₄/Ar environment with a thermobalance. It was observed that carbon deposition preferentially occurred on Ni particles, and the area on which carbon deposited touched the Ni/YSZ interfaces. Meanwhile, carbon deposition was not found on some of the Ni/YSZ interfaces. The Ni/Zr interfaces had various defects, suggesting that the defect pattern may be an important factor for carbon deposition. XANES spectra showed that structural defects and C–H bonds were present in the nascent carbon deposition. As carbon deposition advanced, a graphite structure developed and C–H bonds diminished. Reactants produced from CH₄ cracking converted to a nascent amorphous carbon at the Ni/YSZ interface, and then contributed to the growth of carbon deposition on Ni surfaces, leading to the deposition of carbon encapsulating the Ni particles.     

Biomass fueling of a SOFC by integrated gasifier: Study of the effect of operating conditions on system performance

Biomass gasification can be efficiently integrated with Solid Oxide Fuel Cells (SOFCs) to properly deploy the energy content of this renewable source and increasing the ratio of electric to thermal converted energy. The key objective of this work is to analyze in a systematic and wide process the integration of a biomass gasifier process with the SOFC operation. In particular the work aims at identifying the role of SOFC H₂ utilization as a basic parameter to maximize the system output and avoid gasifier bad operation issues such as tar production and carbon deposition. An efficient simulation framework is used to that purpose allowing for a detailed analysis of the influence of key driving parameters. The performance of the integrated system is thoroughly analyzed in the range of 1–2 kW electric power by also varying the input biomass characteristics in terms of Moisture Content (MC). Results show how a variation of the SOFC H₂ utilization, a parameter whose effects are also correlated with the gasifier air requirement, affects electrical power output also depending on the biomass Moisture Content.     

Structural stability of silver under single-chamber solid oxide fuel cell conditions

In the present study, structural stability of silver under single-chamber conditions has been examined. Micro-tubular cells made of conventional solid oxide fuel cell materials (Ni-YSZ/YSZ/LSM) with silver paste and silver current-collecting wires (for both electrodes) were prepared. The cells were operated with methane/air mixture of 25/60 mL min⁻¹, furnace temperature of 750 °C, and at an operating voltage of 0.5 V. The results showed increasing porosity in the current-collecting silver wire with time, leading to rupture, finally. It is postulated that the porosity formation could be due to the formation of silver oxide which is highly unstable (volatile) at operating temperature considered in this study. Furthermore, vaporization and melting of silver due to cell overheating under mixed-reactant conditions is expected. Based on experimental evidences, it is concluded that silver may not be a good choice to be employed under the above specified operating conditions, as it lacks long-term structural stability.     

Characteristics and performance of lanthanum gallate electrolyte-supported SOFC under ethanol steam and hydrogen

This study is focused on the electrochemical performance of perovskite-type materials based on doped LaGaO₃. La_0.8Sr_0.2Ga_0.8Mg_0.2O_3−δ (LSGM) and La_0.8Sr_0.2Ga_0.8Mg_0.115Co_0.085O_3−δ (LSGMC) were used as electrolytes and (Pr_0.7Ca_0.3)_0.9MnO₃ (PCM) and La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCM) as cathode and anode material, respectively. LSGM and LSGMC electrolytes were prepared by tape casting with a thickness of about 600 μm. The performance of LSCM/LSGMC/PCM was slightly superior to that obtained on LSCM/LSGM/PCM at different temperatures in both humidified hydrogen and ethanol steam atmospheres, good values of power output in LSCM/LSGMC/PCM were 182 and 169 mW cm⁻² using humidified hydrogen and ethanol steam as fuel, respectively, and oxygen as oxidant at 850 °C. Cell stability tests indicate no significant degradation in performance after 60 h of cell testing when LSCM anode was exposed to ethanol steam at 750 °C. Almost no carbon deposits were detected after testing in ethanol steam at 750 °C for >60 h on the LSCM anodes, suggesting that carbon deposition was limited during cell operation.     

Fabrication of bilayered YSZ/SDC electrolyte film by electrophoretic deposition for reduced-temperature operating anode-supported SOFC

Bilayered Y₂O₃-stabilized ZrO₂ (YSZ)/Sm₂O₃-doped CeO₂ (SDC) electrolyte films were successfully fabricated on porous NiO–YSZ composite substrates by electrophoretic deposition (EPD) based on electrophoretic filtration followed by co-firing with the substrates. In EPD, positively charged YSZ and SDC powders were deposited directly on the substrates, layer by layer from ethanol-based suspensions. Delamination between YSZ and SDC films was avoided by reducing the SDC films’ thickness to ca. 1 μm. A single cell was constructed on the bilayered electrolyte films composed of ca. 4 μm-thick YSZ and ca. 1 μm-thick SDC films. As a cathode in the cell, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−x (LSCF) was used. Maximum output power densities greater than 0.6 W cm⁻² were obtained at 700 °C for the bilayered YSZ/SDC electrolyte cells thus constructed.     

Thermodynamic analysis of a proton conducting SOFC integrated system fuelled by different renewable fuels

This work proposes a power generation system consisting of steam reformer and SOFC–H⁺ fuelled by different types of fuel, i.e., ethanol, glycerol and biogas. The performance analysis of integrated system is performed based on thermodynamic calculation through Aspen Plus simulator. The total of the Gibbs free energy minimization is used to determine product composition at equilibrium. The electrochemical model not only considers all voltage losses but also includes the effect of current leakage as a result from the electrolyte used. Considering the operating condition of steam reformer, it is found that the gas product contains the highest amount of hydrogen without the carbon formation when reformer is operated at 973 K with steam to carbon ratio of 1. In addition, the simulation results show that the SOFC–H⁺ operated at 973 K and 1 A/cm² can provide a suitable compromise between system performances and exhaust gas composition. The use of glycerol reformate has the highest cell and system efficiencies and fuel utilization compared to the others. In addition, the integrated system fuelled by glycerol can release low CO amount whereas there is more heat provided to the surrounding. Therefore, it can be concluded that glycerol is suitable renewable fuel for SOFC–H⁺ integrated system.     

Characterization of a 100 W SOFC stack fed by carbon monoxide rich fuels

This paper presents the evaluation of the performance of a 100 W Solid Oxide Fuel Cell (SOFC) stack with CO rich fuels as anode gas. The study aims at measuring the Open Circuit Voltage (OCV) and the Area Specific Resistance (ASR) when the amount of CO in the anode flow varies from 0 to 40% in volume. At the same time, the FCTestQA procedures were applied and evaluated as methodology for Solid Oxide Fuel Cell testing. The theoretical OCV was measured considering both H₂ and CO oxidation and the water gas shift reaction. The OCV values, as a function of CO concentration, resulted closely related to theoretical ones and the ASR value, calculated for different mixtures of fuel, did not change with anode gas composition and it seemed to be a function of the temperature and the degradation of the materials only.     

Fast and stable operation approach of ship solid oxide fuel cell-gas turbine hybrid system under uncertain factors

This work focuses on investigating the adaptability of solid oxide fuel cell-gas turbine (SOFC-GT) hybrid system for ship application under uncertain factors. The effect of rapids, wind and waves on the performance of ship SOFC-GT is analyzed. In addition, a novel control system combining fuzzy logic theory, temperature feedforward and coordination factor on-line adjustment is proposed to address the problem of load disturbances caused by uncertain factors. The results show that the proposed operation strategy can shorten the thermal response time inside fuel cell stacks by almost 49.97%, meanwhile, reducing the maximum temperature changing rate at the electrochemically active tri-layer cell composed of anode, electrolyte, and cathode (PEN structure) by around 17.86%. Moreover, the reasonable matching between air flow and fuel flow is an essential prerequisite to ensure the safe and efficient operation of ship SOFC-GT. While the SOFC-GT is working at full load, the results indicate that the fuel to air ratio cannot exceed 2.56?10^?2 g/g. Finally, an application scenario of the 5000-ton river-to-sea cargo ship sails from Nanjing Port to Yangshan Port (Eastern China) is conducted to analyze the operation characteristics of ship SOFC-GT under uncertain factors. Two set of 1000 kW SOFC-GT systems with the electrical efficiency of 64.66% is designed for the target ship, the results conclude that the operation strategy of each SOFC-GT system supports 50% load is beneficial in reducing the power tracking time and SOFC temperature overshoot. The average electrical efficiency of 61.45% and 61.04% are achieved in winter and summer typical days respectively in the whole voyage.     

Effect of anode structure on performance of cone-shaped solid oxide fuel cells fabricated by phase inversion

Anode-supported cone-shaped tubular solid oxide fuel cells (SOFCs) are successfully fabricated by a phase inversion method. During processing, the two opposite sides of each cone-shaped anode tube are in different conditions--one side is in contact with coagulant (the corresponding surface is named as “W-surface”), while the other is isolated from coagulate (I-surface). Single SOFCs are made with YSZ electrolyte membrane coated on either W-surface or I-surface. Compared to the cell with YSZ membrane on W-surface, the cell on I-surface exhibits better performance, giving a maximum power density of 350 mW cm⁻² at 800 °C, using wet hydrogen as fuel and ambient air as oxidant. AC impedance test results are consistent with the performance. The sectional and surface structures of the SOFCs were examined by SEM and the relationship between SOFC performance and anode structure is analyzed. Structure of anodes fabricated at different phase inversion temperature is also investigated.     

Improvement of output performance of solid oxide fuel cell by optimizing Ni/samaria-doped ceria anode functional layer

Anode functional layers (AFLs) were fabricated using slurry spin coating method on anode substrates to improve the performance of cells based on samaria-doped ceria (SDC) films. The effects of the chemical compositions of AFL and AFL thickness on the performance of solid oxide fuel cell anodes were investigated by studying their effect on the ohmic loss, electrode overpotential, and output performance of cells in different atmospheres. With humidified hydrogen used as fuel and oxygen as oxidant, the cell with an 8-μm-thick AFL (NiO:SDC = 6:4) exhibited excellent maximum power densities of 3.41, 2.89, 1.46 and 0.80 W cm⁻² at 650, 600, 550 and 500 °C, respectively.