Abstract

Solid oxide fuel cells (SOFCs) are high temperature energy conversion devices working efficiently and environmental friendly. SOFC requires a functional cathode with high electrocatalytic activity for the electrochemical reduction of oxygen. The electrode is often fabricated at high temperature to achieve good bonding between the electrode and electrolyte. The high temperature not only limits material choice but also results in coarse particles with low electrocatalytic activity. Nano-structured electrodes fabricated at low temperature by an infiltration/impregnation technique have shown many advantages including superior activity and wider range of material choices. The impregnation technique involves depositing nanoparticle catalysts into a pre-sintered electrode backbone. Two basic types of nano-structures are developed since the electrode is usually a composite consists of an electrolyte and an electrocatalyst. One is infiltrating electronically conducting nano-catalyst into a single phase ionic conducting backbone, while the other is infiltrating ionically conducting nanoparticles into a single phase electronically conducting backbone. In addition, nanoparticles of the electrocatalyst, electrolyte and other oxides have also been infiltrated into mixed conducting backbones. These nano-structured cathodes are reviewed here regarding the preparation methods, their electrochemical performance, and stability upon thermal cycling.

Abstract

Sr₂Fe_1.5Mo_0.5O₆ is a mixed ionic and electronic conductor which can be applied as both cathode and anode material in intermediate-temperature solid oxide fuel cells. To enhance its cathode performance, Ce_0.8Sm_0.2O_1.9 nanoparticles are deposited using ion impregnation technique. Impedance spectroscopy shows that the nanoparticles are very effective in reducing the interfacial polarization resistance from 0.27 Ω cm² to 0.11 Ω cm² at 750 °C. Electrical conductivity relaxation (ECR) measurement demonstrates that the surface exchange coefficient of Sr₂Fe_1.5Mo_0.5O₆ is significantly improved by the nanoparticles, from 10^− 5 to 10^− 3 cms^− 1 at 750 °C. The results suggest that doped ceria nanoparticles are very promising in enhancing the surface exchange processes and consequently can greatly improve the electrode performance.

Graphical abstract

Depositing Ce_0.8Sm_0.2O_1.9 nanoparticles to Sr₂Fe_1.5Mo_0.5O₆ can increase the surface exchange coefficient by two orders of magnitude as determined with electrical conductivity relaxation measurement; from 1.4 × 10^− 5 to 1.0–2.0 × 10^− 3 cm s^− 1 at 750 °C. This demonstrates that doped ceria nanoparticles are very promising in enhancing the electrode kinetic processes and consequently can greatly improve the electrode performance.

Abstract

The electrochemical characteristics of the solid oxide fuel cell (SOFC) cathodes prepared by infiltration of (La_0.85Sr_0.15)_0.9MnO_3−δ (LSM) nanoparticles into porous Y_0.5Bi_1.5O₃ (YSB) backbones are investigated in terms of overpotential, interfacial polarization resistance, and single cell performance obtained with three-electrode cell, symmetrical cell, and single cell, respectively. X-ray diffraction confirms the formation of perovskite LSM by heating the infiltrated nitrates at 800 °C. The electrical conductivity of the electrode measured using Van der Pauw method is 1.67 S cm⁻¹, which is acceptable at the typical SOFC operating temperatures. The single cell with the LSM infiltrated YSB cathode generates maximum power densities of 0.23, 0.45, 0.78, and 1.13 W cm⁻² at 600, 650, 700, and 750 °C, respectively. The oxygen reduction mechanism on the cathode is studied by analyzing the impedance spectra obtained under various temperatures and oxygen partial pressures. The impedance spectra under various cathodic current densities are also measured to study the effect of cathodic polarization on the performance of the cathode.

Abstract

Micro-tubular solid-oxide fuel cell consisting of a 10-μm thick (ZrO₂)_0.89(Sc₂O₃)_0.1(CeO₂)_0.01 (ScSZ) electrolyte on a support NiO/(ScSZ) anode (1.8 mm diameter, 200 μm wall thickness) with a Ce_0.8Gd_0.2O_1.9 (GDC) buffer-layer and a La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)/GDC functional cathode has been developed for intermediate temperature operation. The functional cathode was in situ formed by impregnating the well-dispersed nano-Ag particles into the porous LSCF/GDC layer using a citrate method. The cells yielded maximum power densities of 1.06 W cm⁻² (1.43 A cm⁻², 0.74 V), 0.98 W cm⁻² (1.78 A cm⁻², 0.55 V) and 0.49 W cm⁻² (1.44 A cm⁻², 0.34 V), at 650, 600 and 550 °C, respectively.

Abstract

Novel nano-structured Pd+yttrium doped ZrO₂ (YSZ) electrodes have been developed as cathodes of intermediate temperature solid oxide fuel cells (IT-SOFCs). Nano-sized Pd particles were introduced into the rigid and porous YSZ structure by PdCl₂ solution impregnation. The results show that Pd nanoparticles (20–80 nm) were uniformly distributed in the porous YSZ structure; and such nano-structured composite cathodes were highly active for the O₂ reduction reaction, with polarization resistances (R_E) of 0.11 and 0.22 Ω cm² at 750 and 700 °C and activation energy of 105 kJ mol⁻¹ that is significantly lower than those for the conventional perovskite-based cathodes (130–201 kJ mol⁻¹).

Abstract

Taking Y₂O₃ stabilized Bi₂O₃ (YSB) as an example, bismuth oxide-added (La,Sr)MnO₃ (LSM) is evaluated as a cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs) with 8 mol% Y₂O₃ stabilized ZrO₂ (YSZ) electrolytes. YSB was added to LSM cathodes using an impregnation method, dramatically improving the electrode performance. The interfacial polarization resistance R_p, at 700 °C for the electrode coated with 50 wt.% of YSB is 0.14 Ω cm², which is only 0.2% of the value for a pure LSM electrode. The high oxygen ionic conductivity and the catalytic activity of YSB, as well as the favorable electrode microstructure are likely reasons for the dramatic reduction of R_p. The YSB-added LSM cathodes also exhibited lower overpotential and higher exchange current density than the pure LSM cathode. Moreover, these electrodes show much lower R_p than that of parallel-fabricated LSM electrodes with samaria-doped-CeO₂ as well as other LSM-based electrodes reported in the literature, demonstrating the superiority of the of YSB as the ionic conduction component in composite LSM electrodes. The superior performance of the single cell further demonstrates that the bismuth oxide-added LSM cathode is an excellent candidate for IT-SOFCs.

Abstract

The grain coarsening in dense nanocrystalline gadolinia-doped ceria (CGO) and CeO₂ was studied for the grain size regime from 10 to 250 nm. Dense ceria-based thin films were prepared by spray pyrolysis and pulsed laser deposition on sapphire substrates. The small grain-sized CGO and CeO₂ microstructures were surprisingly stable and showed self-limited grain growth and relaxation of the microstrain with time. In this regime, material transport occurs via grain boundary diffusion leading to densification and grain coarsening in the thin films. A continuous transition to common grain growth kinetics was observed for larger grains at higher temperatures.

Abstract

It is well known that the most widely used distribution function for fiber tensile strength, the two-parameter Weibull distribution, does not always adequately describe the experimentally observed fiber strength scatter and the strength dependence on fiber length. To remedy this discrepancy, modifications of the Weibull distribution have been proposed that, while providing a good empirical fit to the strength data, sometimes lack the theoretical appeal of the weakest link models. We derive a family of weakest link models based on the assumption of a two-stage failure process incorporating explicitly the probabilities of flaw initiation and the fiber fracture due to the largest flaw (i.e. the weakest link). The model is verified against a sample of E-glass fiber strength data at different gauge lengths and shown to provide a reasonably good fit to the test results.

Abstract

The physical sources of randomness in quasibrittle fracture described by the cohesive crack model are discussed and theoretical arguments for the basic form of the probability distribution are presented. The probability distribution of the size effect on the nominal strength of structures made of heterogeneous quasibrittle materials is derived, under certain simplifying assumptions, from the nonlocal generalization of Weibull theory. Attention is limited to structures of positive geometry failing at the initiation of macroscopic crack growth from a zone of distributed cracking. It is shown that, for small structures, which do not dwarf the fracture process zone (FPZ), the mean size effect is deterministic, agreeing with the energetic size effect theory, which describes the size effect due to stress redistribution and the associated energy release caused by finite size of the FPZ formed before failure. Material randomness governs the statistical distribution of the nominal strength of structure and, for very large structure sizes, also the mean. The large-size and small-size asymptotic properties of size effect are determined, and the reasons for the existence of intermediate asymptotics are pointed out. Asymptotic matching is then used to obtain an approximate closed-form analytical expression for the probability distribution of failure load for any structure size. For large sizes, the probability distribution converges to the Weibull distribution for the weakest link model, and for small sizes, it converges to the Gaussian distribution justified by Daniels' fiber bundle model. Comparisons with experimental data on the size-dependence of the modulus of rupture of concrete and laminates are shown. Monte Carlo simulations with finite elements are the subject of ongoing studies by Pang at Northwestern University to be reported later.