The individual electrode processes from anode and cathode have been clearly identified from practical impedance spectra with high-frequency inductive impedances for the Mitsubishi segmented-in-series tubular solid oxide fuel cell by combining the distribution of relaxation time analysis and the complex nonlinear least square fitting. Anodic gas diffusion process and charge transfer reaction near anodic triple phase boundary appear at ∼0.3 and 1000Hz , respectively. Cathodic oxygen reduction processes appear at ∼10Hz at 700°C , whereas the impedance arc over 10000Hz is dominated by the cathodic oxygen ion transfer through the (normalLa,normalSr)normalMnO3 (LSM)/ normalY2normalO3 -stabilized normalZrO2 (YSZ) interface and YSZ of the composite. The results also exhibit an excellent agreement with those from the analysis of difference in impedance spectra.
Long-term performance testes by CRIEPI (Central Research Institute for Electric Power Industry) on six industrial stacks have revealed an interesting correlation between cathode polarization loss and ohmic loss. To make clear the physicochemical meaning of this correlation, detailed analyses were made on the conductivity degradation of YSZ electrolyte in button cells and then on the ohmic losses in the industrial cells in terms of time constants which are determined from speed of the tetragonal transformation through the Y diffusion from the cubic phase to the tetragonal phase. In some cases, shorter time constants (faster degradations) were detected than those expected from the two-time-constant (with and without NiO reduction effects) model, suggesting that additional ohmic losses after subtracting the contribution from the tetragonal transformation must be caused from other sources such as cathode-degradation inducing effects. Main cathode degradations can be ascribed to sulfur poisoning due to contamination in air in the CRIEPI test site. An important feature was extracted as this cathode degradations became more severe when the gadolinium-doped ceria (GDC) interlayers were fabricated into dense film. Plausible mechanisms for cathode degradations were proposed based on the Sr/Co depletion on surface of lanthanum strontium cobalt ferrite (LSFC) in the active area. Peculiar cathode degradations found in stacks are interpreted in term of changes in surface concentration by reactions with sulfur oxide, electrochemical side reactions for water vapor emission or Sr volatilization, and diffusion of Sr/Co from inside LSCF.
Recent progress of the NEDO project on durability/reliability of SOFC stacks is reported with an emphasis on the achievement of Mitsubishi Heavy Industries' segment‐in‐series cells in which the lanthanum manganite cathode has been improved. Durability tests were made by CRIEPI on their cells with/without doped ceria interlayer to check plausible effects of microstructure change and of chromium poisoning. Improved cells exhibit essentially no degradation for 10,000 h and also strong tolerance against the Cr contamination from stainless steel tubes. These features are discussed within the generalized degradation model developed inside the NEDO project. In particular, the extremely small overpotential can be considered to be effective in lowering the Cr poisoning by reducing the driving forces for the electrochemical Cr deposition at active sites. Insertion of doped ceria is also useful in preventing the Cr deposition or enhancing the volatilization of deposited Cr with cathodically emitted water vapors from ceria. Thermodynamic considerations reveal that the initial composition of LSM cathode is important to determine the microstructure change due to the chromium dissolution into the B‐sites in the perovskite lattice. Discussions are made on a role of doped ceria to prevent deterioration of Mn‐dissolved electrolyte by lowering the Mn dissolution into YSZ.
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Gas phase transport is a very important electrode process in practical solid oxide fuel cells. In this study, we have identified gas conversion impedance and gas diffusion impedance in the Mitsubishi segmented-in-series tubular solid oxide fuel cell. Gas conversion impedance is caused by the weak convection transport in the gas flow channel. It is observed that both the insufficient anode and cathode gas flow rates can result in the gas conversion impedance. Gas conversion impedance appears at less than 0.1 Hz, and its magnitude strongly depends on the gas flow rates. It disappears when the gas flow rates of both the anode and cathode are improved sufficiently. Anode gas diffusion through the porous substrate appears at ϳ0.5 Hz and dominates the overall diffusion impedance. Cathode gas diffusion through the porous current collecting layer appears at ϳ3 Hz, which significantly contributes to the overall gas diffusion impedance under low cathode oxygen partial pressures.
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