CeO2 based materials doped with lanthanides for applications in intermediate temperature electrochemical devices

The present work aims at the investigation of the influence of different dopants’ ionic radius and concentration on the lattice parameters and the density of Ce_1−xLn_xO_2−δ (x = 0-0.20; Ln = La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb) solid solutions. Moreover, the temperature dependence of the linear expansion of Ce_0.8Ln_0.2O_2−δ ceramics is examined in the range of 300-1173 K and the respective thermal expansion coefficients are calculated. Finally, the total electrical conductivity of Ce_1−xLn_xO_2−δ (x = 0.15-0.20) and multi-component Ce_(1−x)Ln_x/2Ln’_x/2O_2−δ (x = 0.20; Ln = Sm, La, Gd, Dy and Ln’ = Dy, Nd, Er, Y) systems is studied in a wide range of temperatures in air atmosphere, as well as in a wide range of oxygen partial pressures at 1023 K and 1173 K. According to the experimental results of the present work, at the highest examined temperature of 1173 K and in air atmosphere, the maximum values of total electrical conductivity are observed in the cases of Ce_0.8Nd_0.2O_2−δ and Ce_0.8Sm_0.2O_2−δ.     

Thermal, electrical and electrochemical characteristics of Ba1−xSrxCo0.8Fe0.2O3−δ cathode material for intermediate temperature solid oxide fuel cells

Ba_1−xSr_xCo_0.8Fe_0.2O_3−δ (x = 0.3-0.9) perovskite oxides have been studied as cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs). The structural characteristics, temperature dependent weight loss, thermal expansion, electrical conductivity, and electrochemical properties in combination with YSZ electrolyte together with an SDC buffer layer were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TG), dilatometry, DC four probe conductivity measurement and electrochemical impedance spectroscopy (EIS) techniques respectively. XRD study revealed the lattice parameter and unit cell volume decrease with increase in Sr⁺² content at the A-site. TEC and electrical conductivity were found to increase with increasing Sr⁺² content. Electrical conductivity was found to be dependent on the thermal history of the samples. Polarization resistance of the samples with SDC buffered YSZ electrolyte decreased with increasing Sr⁺² content which was ascribed to the higher conductivity with improved oxygen adsorption/desorption and oxygen ions diffusion processes. The intrinsic oxygen reduction reaction rate also increased with Sr⁺² content at the A-site. The exchange current for intrinsic oxygen reduction reaction at 700 °C was found to be 50.0 mA cm⁻² for Ba_0.3Sr_0.7Co_0.8Fe_0.2O_3−δ; a value which is about 50% higher than that for Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ, a widely studied cathode material. Therefore, the present composition may be a potential cathode material for IT-SOFC application.     

Synthesis, characterization and evaluation of PrBaCo2−xFexO5+δ as cathodes for intermediate-temperature solid oxide fuel cells

Iron doped layered structured perovskites, PrBaCo_2−xFe_xO_5+δ (x = 0, 0.5, 1.0, 1.5 and 2.0), are evaluated as cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The effects of dopant content are investigated on their structural and electrochemical properties including crystalline structure, oxygen nonstoichiometry, stability in presence of CO₂, compatibility with electrolytes, thermal expansion coefficient, electrical conductivity, and cathodic interfacial polarization resistance. The lattice parameter and oxygen nonstoichiometry content, δ, at room temperature increase, whereas the conductivity, thermal expansion coefficient, and cathodic performance decrease with increasing iron content, x. PrBaCo_2−xFe_xO_5+δ exhibit excellent stability at 700 °C in atmosphere consisting of 3% CO₂ and 97% air, show good chemical compatibility with doped ceria electrolytes at 1000 °C, but react readily with yttria-stabilized zirconia at 700 °C. Even with a Co-free PrBaFe₂O_5+δ as the electrode, a symmetrical cell demonstrates area specific resistance of 0.18 Ω cm² at 700 °C with samaria-doped ceria electrolyte. The resistance is lower than those for typical Co-free electrodes reported in the literatures, suggesting that PrBaCo_2−xFe_xO_5+δ are potential promising cathode materials for IT-SOFCs.     

Performances of LnBaCo2O5+x-Ce0.8Sm0.2O1.9 composite cathodes for intermediate-temperature solid oxide fuel cells

Double-perovskite oxides, LnBaCo₂O_5+x (LnBCO) (Ln = Pr, Nd, Sm, and Gd), are prepared using a solid-state reaction as cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The performances of LnBCO-Ce_0.8Sm_0.2O_1.9 (SDC) composite cathodes were investigated for IT-SOFCs on La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte. The thermal expansion coefficient can be effectively reduced in the case of the composite cathodes. No chemical reactions between LnBCO cathodes and SDC electrolyte, and LnBCO and LSGM are found. The electrochemical performances of LnBCO cathodes and LnBCO-SDC composite cathodes decrease with decreasing Ln³⁺ ionic radii, which is closely related to the decrease of the electrical conductivity and fast oxygen diffusion property. The area specific resistances of the LnBCO cathodes and LnBCO-SDC composite cathodes on LSGM electrolyte are all lower than 0.13 Ω cm² and 0.15 Ω cm² at 700 °C, respectively. The maximum power densities of single-cell consisted of LnBCO-SDC composite cathodes, LSGM electrolyte, and Ni-SDC anode achieve 758-608 mW cm⁻² at 800 °C with the change from Ln = Pr to Gd, respectively. These results indicate that LnBCO-SDC composite oxides are candidates as a promising cathode material for IT-SOFCs.     

Double-perovskites YBaCo2−xFexO5+δ cathodes for intermediate-temperature solid oxide fuel cells

Double-perovskites YBaCo_2−xFe_xO_5+δ (YBCF, x = 0.0, 0.2, 0.4 and 0.6) are synthesized with a solid-state reaction and are assessed as potential cathode materials for utilization in intermediate-temperature solid oxide fuel cells (IT-SOFCs) on the La_0.9Sr_0.1Ga_0.8Mg_0.115Co_0.085O_2.85 (LSGMC) electrolyte. The YBCF materials exhibit chemical compatibility with the LSGMC electrolyte up to a temperature of 950 °C. The conductivity of the YBCF samples decreases with increasing Fe content, and the maximum conductivity of YBCF is 315 S cm⁻¹ at 325 °C for the x = 0.0 sample. A semiconductor-metal transition is observed at about 300-400 °C. The thermal expansion coefficient of the YBCF samples increases from 16.3 to 18.0 × 10⁻⁶ K⁻¹ in air at temperatures between 30 and 900 °C with increase in Fe content. The area-specific resistances of YBCF cathodes at x = 0.0, 0.2 and 0.4 on the LSGMC electrolyte are 0.11, 0.13 and 0.15 Ω cm² at a temperature of 700 °C, respectively. The maximum power densities of the single cells fabricated with the LSGMC electrolyte, Ce_0.8Sm_0.2O_1.9 (SDC) interlayer, NiO/SDC anode and YBCF cathodes at x = 0.0, 0.2 and 0.4 reach 873, 768 and 706 mW cm⁻², respectively. This study suggests that the double-perovskites YBCF (0 ≤ x ≤ 0.4) can be potential candidates for utilization as IT-SOFC cathodes.     

Electrochemical performance of La2Cu1−xCoxO4 cathode materials for intermediate-temperature SOFCs

K₂NiF₄-type structure oxides La₂Cu_1−xCo_xO₄ (x = 0.1, 0.2, 0.3) are synthesized and evaluated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). The materials are characterized by XRD, SEM and electrochemical impedance spectrum (EIS), respectively. The results show that no reaction occurs between La₂Cu_1−xCo_xO₄ electrode and Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte at 1000 °C. The electrode forms good contact with the electrolyte after sintering at 800 °C for 4 h in air. The electrode properties of La₂Cu_1−xCo_xO₄ are studied under various temperatures and oxygen partial pressures. The optimum composition of La₂Cu_0.8Co_0.2O₄ results in 0.51 Ω cm² polarization resistance (R_p) at 700 °C in air. The rate limiting step for oxygen reduction reaction (ORR) is the charge transfer process. La₂Cu_0.8Co_0.2O₄ cathode exhibits the lowest overpotential of about 50 mV at a current density of 48 mA cm⁻² at 700 °C in air.     

Characterization of La2−xSrxCoTiO6 (0.6 ≤ x ≤ 1.0) series as new cathodes of solid oxide fuel cells

La_2−xSr_xCoTiO₆ (0.6 ≤ x ≤ 1.0) compound series is prepared by Sr-substitution in the A-site of the perovskite by a modified Pechini procedure under air. Charge compensation as Sr²⁺ content increase occurs by Co²⁺ oxidation to Co³⁺. Reduced samples are obtained by further treatment under 5%H₂/Ar and characterized by Neutron Powder Diffraction. Upon redution, Co³⁺ to Co²⁺ reduction and oxygen vacancies creation are detected. Dependence of total conductivity with temperature and pO₂ exhibits a typical p-type semiconducting behaviour. Results show that the higher the Sr content, the higher holes (Co³⁺) concentration and consequently, La_2−xSr_xCoTiO₆ (x = 1.0) shows the highest conductivity (13.23 S/cm at 1073 K in air). The negligible reactivity with YSZ, used as the electrolyte, of symmetrical cells under oxidant conditions and the moderate thermal expansion found by XRD point to their possible use as SOFC cathodes. Thus, La_1.2Sr_0.8CoTiO₆-based cathodes display polarization resistance of 0.9 Ω cm² at 1073 K in oxygen, only slightly above than the current state-of-the-art.     

Preparation and electrochemical properties of strontium doped Pr2NiO4 cathode materials for intermediate-temperature solid oxide fuel cells

Pr_2−xSr_xNiO₄ (PSNO, x = 0.3, 0.5 and 0.8) cathode materials for intermediate-temperature solid oxide fuel cell (IT-SOFC) were synthesized by a glycine-nitrate process using Pr₆O₁₁, Ni(NO₃)₂·6H₂O and SrCO₃ powders as raw materials. Phase structure of the synthesized powders was characterized by X-ray diffraction analysis (XRD). Microstructure of the sintered PSNO samples was observed and thermal expansion coefficient (TEC) and electrical conductivity were investigated. Electrochemical impedance spectroscopy (EIS) measurement of the PSNO materials on Sm_0.2Ce_0.8O_1.9 (SCO) electrolyte was carried out, and single cells based on the PSNO cathodes were also assembled and their performances were tested. The results show that the synthesized PSNO powders have pure K₂NiF₄-type structure and the PSNO materials are chemically stable with Sm_0.2Ce_0.8O_1.9 (SCO) electrolyte. The sintered PSNO samples have porous and fine microstructure with pore size smaller than 1 μm. Average thermal expansion coefficient of the PSNO materials is about 12–13 × 10⁻⁶ K⁻¹ at 200–800 °C and the electrical conductivity is in the range of 70–120 Scm⁻¹ at 800 °C. Area specific resistance (ASR) of the Pr_2−xSr_xNiO₄ materials on SCO electrolyte is 0.407 Ωcm², 0.126 Ωcm² and 0.112 Ωcm² for x = 0.3, 0.5 and 0.8 at 800 °C, respectively. Maximum open circuit voltage (OCV) and power density of the single NiO-SCO/SCO/PSNO cells are 0.75 V and 298 mWcm⁻² at 700 °C, respectively, which indicates that Pr_2−xSr_xNiO₄ may be a potential cathode material for IT-SOFC.     

Preparation and characterization of Pr1−xSrxFeO3 cathode material for intermediate temperature solid oxide fuel cells

A kind of cathode material of Pr_1−xSr_x FeO₃ (x = 0–0.5) for intermediate temperature solid oxide fuel cells (IT-SOFCs) was prepared by the coprecipitation method. Crystal structure, thermal expansion, electrical conductivity and electrochemical performance of the Pr_1−xSr_xFeO₃ perovskite oxide cathodes were studied by different methods. The results revealed that Pr_l−xSr_xFeO₃ exhibited similar orthorhombic structure from x = 0.1 to 0.3 and took cubic structure when x = 0.4–0.5. The unit cell volume decreased and the thermal expansion coefficient (TEC) of the materials increased as the strontium content increased. When 0 < x ≤ 0.3, the samples exhibited good thermal expansion compatibility with YSZ electrolyte. The electrical conductivity increased with the increasing of doped strontium content. When x = 0.3–0.5, the electrical conductivities were higher than 100 S cm⁻¹. The conductivity of Pr_0.8Sr_0.2FeO₃ was 78 S cm⁻¹ at 800 °C. Compared with the La_0.8Sr_0.2MnO₃ cathode, Pr_0.8Sr_0.2FeO₃ showed higher polarization current density and lower polarization resistance (0.2038 Ω cm²). The value of I₀ for Pr_0.8Sr_0.2FeO₃ at 800 °C is 123.6 mA cm⁻². It is higher than that of La_0.8Sr_0.2MnO₃. Therefore, Pr_1−xSr_xFeO₃ can be considered as a candidate cathode material for IT-SOFCs.     

Electrical conduction behavior of proton conductor BaCe1-xSmxO3-δ in the intermediate temperature range

Determining the relationship between electrical conductivity and doping level in high temperature proton conductors is of great significance to accelerate their process of practicality and develop new applications. In this work, BaCe_1-xSm_xO_3-δ (x = 0.01-0.50) was synthesized via citric-nitrate method and their electrical conduction behavior in 5% H₂/Ar in the intermediate temperature range was investigated. The solubility of Sm in BaCeO₃ was between 0.30 and 0.40. Both the bulk and the grain boundary conductivity increased with Sm content up to x = 0.20 and then decreased. The infrared spectra results indicated that the degree of hydrogen bonding decreased with Sm content (x = 0.20-0.30), which should be responsible for the descending bulk conductivity of samples with x = 0.25 and 0.30. BaCe_0.80Sm_0.20O_3-δ, with electrical conductivity of 0.017 S cm⁻¹ at 600 °C, was a promising electrolyte for intermediate temperature solid oxide fuel cells.     

Preparation and characterization of Ce1−x(Gd0.5Pr0.5)xO2 electrolyte for IT-SOFCs

The Ce_1−x(Gd_0.5Pr_0.5)_xO₂ (x = 0–0.24) compositions were synthesized through the sol–gel process followed by low temperature combustion. X-ray diffraction data analysis showed that all the samples exhibit a cubic structure with single phase. The lattice parameter was calculated by rietveld refinement of XRD patterns. Dense ceramics were prepared by sintering the pellets at 1300 °C. The relative density of the samples was over 98%. The surface morphology was studied by Scanning electron microscopy (SEM). Chemical composition was analyzed by Energy dispersive spectroscopy (EDX). A.C. impedance spectroscopy measurements were carried out to study the grain, grain boundary and total ionic conductivity of co-doped ceria samples in the temperature range 150–700 °C. The Ce_0.84(Gd_0.5Pr_0.5)_0.16O₂ composition showed highest grain ionic conductivity i.e., 1.059 × 10⁻² S/cm at 500 °C which is 11.5% higher than the Ce_0.9Gd_0.1O₂ (with an activation energy 0.62 eV). At intermediate temperatures, the Ce_1−x(Gd_0.5Pr_0.5)_xO₂ materials were found to be ionic in nature.     

Sr1−xPrxCo0.95Sn0.05O3−δ ceramic as a cathode material for intermediate-temperature solid oxide fuel cells

In this study, the physical properties of the Sr_1−xPr_xCo_0.95Sn_0.05O_3−δ ceramics were measured and their potential for use as a cathode material of intermediate-temperature solid oxide fuel cells (IT-SOFCs) was evaluated. A cubic phase was retained in all of the Sr_1−xPr_xCo_0.95Sn_0.05O_3−δ ceramics. Analysis of the temperature-dependent conductivity found the SrCo_0.95Sn_0.05O_3−δ and Sr_0.9Pr_0.1Co_0.95Sn_0.05O_3−δ ceramics exhibiting semiconductor-like behavior below 550 °C and metal-like behavior above the same temperature. The Sr_0.8Pr_0.2Co_0.95Sn_0.05O_3−δ and Sr_0.7Pr_0.3Co_0.95Sn_0.05O_3−δ ceramics, however, reported a metal-like conductivity in the whole temperature range. The electrical conductivities of the Sr_0.8Pr_0.2Co_0.95Sn_0.05O_3−δ ceramic at 500 °C and 700 °C read respectively 1250 S/cm and 680 S/cm, both of which were superior than those in most of the common perovskites. Single cells with a structure of NiO–Sm_0.2Ce_0.8O_2−δ (SDC)/SDC/Sr_0.8Pr_0.2Co_0.95Sn_0.05O_3−δ-SDC were built and characterized. Addition of SDC in Sr_0.8Pr_0.2Co_0.95Sn_0.05O_3−δ emerged to be a crucial factor reducing the ohmic resistance (R₀) and polarization resistance (R_P) of the cell by facilitating a better adhesion to and electrical contact with the electrolyte layer. The R₀ and R_P of the cell read respectively 0.068 Ω cm² and 0.0571 Ω cm² at 700 °C and 0.298 Ω cm² and 1.310 Ω cm² at 550 °C. With no microstructure optimization and hermetic sealing of the cells, maximum power density (MPD) and open circuit voltage (OCV) reached respectively 0.872 W/cm² and 0.77 V at 700 °C and 0.482 W/cm² and 0.86 V at 550 °C. It is evident that Sr_1−xPr_xCo_0.95Sn_0.05O_3−δ is a promising cathode material for IT-SOFCs.     

Electrochemical behavior of Ba0.5Sr0.5Co0.2−xZnxFe0.8O3−δ (x = 0-0.2) perovskite oxides for the cathode of solid oxide fuel cells

Zinc-doped barium strontium cobalt ferrite (Ba_0.5Sr_0.5Co_0.2−xZn_xFe_0.8O_3−δ (BSCZF), x = 0, 0.05, 0.1, 0.15, 0.2) powders with various proportions of zinc were prepared using the ethylenediamine tetraacetic acid (EDTA)-citrate method with repeated ball-milling and calcining. They were then evaluated as cathode materials for solid oxide fuel cells at intermediate temperatures (IT-SOFCs) using XRD, H₂-TPR, SEM, and electrochemical tests. By varying the zinc doping (x) from zero to 0.2 (as a substitution for cobalt which ranged from zero to 100%), it was found that the lowest doping of 0.05 (BSCZF05) resulted in the highest electrical conductivity of 30.7 S cm⁻¹ at 500 °C. The polarization resistances of BSCZF05 sintered at 950 °C were 0.15 Ω cm², 0.28 Ω cm² and 0.59 Ω cm² at 700 °C, 650 °C and 600 °C, respectively. The resistance decreased further by about 30% when Sm_0.2Ce_0.8O_2−δ (SDC) electrolyte particles were incorporated and the sintering temperature was increased to 1000 °C. Compared to BSCF without zinc, BSCZF experienced the lowest decrease in electrochemical properties when the sintering temperature was increased from 950 °C to 1000 °C. This decrease was due to an increase in thermal stability and a minimization in the loss of some cobalt cations without a decrease in the electrical conductivity. Using a composite cathode of BSCZF05 and 30 wt.% of SDC, button cells composed of an Ni-SDC support with a 30 μm dense SDC membrane exhibited a maximum power density of 605 mW cm⁻² at 700 °C.     

Electrode properties of Co-doped Ca2Fe2O5 as new cathode materials for intermediate-temperature SOFCs

Brownmillerite oxide Ca₂Fe_2−xCo_xO₅ (x = 0.2, 0.4, 0.6) was characterized by XRD, SEM and electrochemical impedance spectrum (EIS), respectively. Ca₂Fe_2−xCo_xO₅ has no reaction with Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte at 1100 °C for 10 h in air. The thermal expansion coefficient (TEC) of Ca₂Fe_2−xCo_xO₅ increased with increasing Co content, and the TEC value was compatible with SDC. The electrode properties of Ca₂Fe_2−xCo_xO₅ were studied under various temperatures and oxygen partial pressures. The polarization resistance (R_p) of Ca₂Fe_2−xCo_xO₅ with x = 0.2, 0.4 and 0.6 are 0.23, 0.48 and 1.05 Ω cm² at 700 °C in air, respectively. The rate-limiting step for oxygen reduction reaction was the charge transfer process. Ca₂Fe_1.8Co_0.2O₅ cathode exhibits the lowest overpotential of about 50 mV at a current density of 70 mA cm⁻² at 700 °C in air.     

New Nb-doped SrCo1−xNbxO3−δ perovskites performing as cathodes in solid-oxide fuel cells

The high-temperature cubic phase of SrCoO_3−δ is a promising cathode material for solid oxide fuel cells (SOFC) due to its high electrical conductivity and oxygen permeation flux. However, this phase is not stable below 900 °C where a 3C-cubic to 2H-hexagonal phase transition takes place when the sample is slowly cooled down. In this work we have stabilized a 3C-tetragonal P4/mmm structure for SrCo_1−xNb_xO_3−δ with x = 0.05. We have followed the strategy consisting of introducing a highly-charged cation at the Co sublattice, in order to avoid the stabilization of the unwanted 2H structure containing face-sharing octahedra. The characterization of this oxide included X-ray (XRD) and neutron powder diffraction (NPD) experiments. SrCo_0.95Nb_0.05O_3−δ adopts a tetragonal superstructure of perovskite with a = a₀, c = 2a₀ (a₀ ≈ 3.9 Å) defined in the P4/mmm space group containing two inequivalent Co positions. Flattened and elongated (Co,Nb)O₆ octahedra alternate along the c axis sharing corners in a three-dimensional array (3C-like structure). In the test cell, the electrodes were supported on a 300-μm-thick pellet of the electrolyte La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ (LSGM). The test cells gave a maximum power density of 0.4 and 0.6 W/cm² for temperatures of 800 and 850 °C, respectively, with pure H₂ as fuel and air as oxidant. The good performance of this material as a cathode is related to its mixed electronic-ionic conduction (MIEC) properties, which can be correlated to the investigated structural features: the Co³⁺/Co⁴⁺ redox energy at the top of the O-2p bands accounts for the excellent electronic conductivity, which is favored by the corner-linked perovskite network. The considerable number of oxygen vacancies, with the oxygen atoms showing high displacement factors suggests a significant ionic mobility.     

Assessment of perovskite-type La0.8Sr0.2ScxMn1−xO3-δ oxides as anodes for intermediate-temperature solid oxide fuel cells using hydrocarbon fuels

Composites formed by the infiltration of 40 wt% La_0.8Sr_0.2Sc_xMn_1−xO_3-δ (LSSM) oxides (x = 0.1, 0.2, 0.3) into 65% porous yttria-stabilized zirconia (YSZ) are investigated as anode materials for intermediate-temperature solid oxide fuel cells for hydrocarbon oxidation. The oxygen non-stoichiometry and electrical conductivity of each LSSM-YSZ composite are determined by coulometric titration. As the concentration of Sc increases, the composites show higher phase stability and the electrical conductivity of LSSM is significantly affected by the Sc doping, the non-stoichiometric oxygen content, and oxygen partial pressure (p(O₂)). To achieve better electrochemical performance, it is necessary to add ceria-supported palladium catalyst for operation with humidified CH₄. Anode polarization resistance increases with Sc doping due to a decrease in electrical conductivity. An electrolyte-supported cell with a LSSM-YSZ composite anode delivers peak power densities of 395 and 340 mW cm⁻² at 923 K in humidified (3% H₂O) H₂ and CH₄, respectively, at a flow rate of 20 mL min⁻¹.     

A fundamental study of chromium deposition and poisoning at (La0.8Sr0.2)0.95(Mn1−xCox)O3 ± δ (0.0≤ x ≤1.0) cathodes of solid oxide fuel cells

Fundamental understanding of the chromium deposition and poisoning is very important in the development of intermediate temperature solid oxide fuel cells (IT-SOFCs) based on metallic interconnect. In this paper, chromium deposition and poisoning at the (La_0.8Sr_0.2)_0.95(Mn_1−xCo_x)O_3 ± δ (LSMC, 0.0 ≤ x ≤ 1.0) cathodes are systematically studied in the presence of a chromia-forming metallic interconnect under SOFC operation conditions. The results show that as the B-site Mn is substituted by Co, electrochemical activity of the cathodes for the O₂ reduction reaction increases due to the increased oxygen exchange coefficient and oxygen diffusion coefficient as a result of the increased oxygen vacancies of the LSMC perovskite. However, in the presence of a chromia-forming metallic interconnect, chromium deposition on the electrolyte surface in contact with the LSMC electrode decreases while on the electrode surface it increases as Co content in LSMC increases from 0.0 to 1.0. On the other hand, the chromium poisoning effects as measured by the increase in the overpotential and electrode polarization resistance are most pronounced for the LSMC cathode with x = 0.4. The occurrence of the maximum chromium poisoning is most likely due to combined poisoning effect of the Cr deposits at the electrode surface and electrolyte surface on the kinetics of the O₂ reduction reactions. The results clearly indicate that the increase in the electrochemical activity of the cathode does not necessarily lead to the reduction in the chromium deposition. Rather, the changes in the electrochemical activity of the LSMC cathodes simply change the distribution pattern of chromium deposition on the electrode and electrolyte surface. Chromium deposition at LSMC cathode is closely related to the chemical affinity and stability of the manganese and strontium species, which depends significantly on the Co/Mn ratio at the B-site of the LSMC perovskite.     

Ionic conduction in Sn1−xScxP2O7 for intermediate temperature fuel cells

A novel series of mixed ion conductors, Sn_1−xSc_xP₂O₇ (x = 0.03, 0.06, 0.09, 0.12), were synthesized by a solid-state reaction method. The conduction behaviors of the ion conductors in wet hydrogen atmosphere were investigated by some electrochemical methods including AC impedance spectroscopy, gas concentration cells in the temperature range of 323-523 K. It was found that the doping limit of Sc³⁺ in SnP₂O₇ was between 9 mol% and 12 mol%. The highest conductivity was observed to be 2.76 × 10⁻² S cm⁻¹ for the sample of x = 0.06 under wet H₂ atmosphere at 473 K. The ionic conduction was contributed mainly to proton and partially to oxide ion in wet hydrogen atmosphere from 373 K to 523 K. The H₂/air fuel cells using Sn_1−xSc_xP₂O₇ (x = 0.03, 0.06, 0.09) as electrolytes (1.7 mm in thickness) generated the maximum power densities of 11.16 mW cm⁻² for x = 0.03, 25.02 mW cm⁻² for x = 0.06 and 14.34 mW cm⁻² for x = 0.09 at 423 K, respectively. The results indicated that Sn_1−xSc_xP₂O₇ is a promising solid electrolyte system for intermediate temperature fuel cells.     

Evaluation and optimization of Bi1−xSrxFeO3−δ perovskites as cathodes of solid oxide fuel cells

Lattice expansion behaviour, oxygen nonstoichiometry, mean iron oxidation state, electrical conductivity and interfacial polarization resistance of Bi_1−xSr_xFeO_3−δ were reported as a function of Sr-doping content for x = 0.3, 0.5 and 0.8. Among the series, Bi_0.5Sr_0.5FeO_3−δ (BSF5) demonstrates the optimum performance in terms of the lowest interfacial polarization resistance and the largest oxygen nonstoichiometry. It is demonstrated that the best microstructure and the lowest interfacial resistance can be obtained by firing BSF5 onto dense Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte at 1000 °C. BSF5 exhibits good chemical compatibility with SDC; however, firing temperature above 1000 °C results in the formation of bismuth-deficient perovskite with inferior activity for oxygen reduction reaction. We also show that single-phase BSF5 cathode provides better electrode performance than its composite with SDC. This is due to the increased charge-transfer resistance upon adding SDC which have negligible electronic conductivity.     

Electrochemical performance of Ba0.5Sr0.5CoxFe1−xO3−δ (x = 0.2–0.8) cathode on a ScSZ electrolyte for intermediate temperature SOFCs

Intermediate temperature solid oxide fuel cell cathode materials (Ba, Sr)Co_xFe_1−xO_3−δ [x = 0.2–0.8] (BSCF), were synthesized by a glycine-nitrate process (GNP) using Ba(NO₃)₂, Sr(NO₃)₂, Co(NO₃)₂·6H₂O, and Fe(NO₃)₃·9H₂O as starting materials and glycine as an oxidizer and fuel. Electrolyte-supported symmetric BSCF/GDC/ScSZ/GDC/BSCF cells consisting of porous BSCF electrodes, a GDC buffer layer, and a ScSZ electrolyte were fabricated by a screen printing technique, and the electrochemical performance of the BSCF cathode was investigated at intermediate temperatures (500–700 °C) using AC impedance spectroscopy. Crystallization behavior was found to depend on the pH value of the precursor solution. A highly acidic precursor solution increased the single phase perovskite formation temperature. In the case of using a precursor solution with pH 2, a single perovskite phase was obtained at 1000 °C. The thermal expansion coefficient of BSCF was gradually increased from 24 × 10⁻⁶ K⁻¹ for BSCF (x = 0.2) to 31 × 10⁻⁶ K⁻¹ (400–1000 °C) for BSCF (x = 0.8), which resulted in peeling-off of the cathode from the GDC/ScSZ electrolyte. Only the BSCF (x = 0.2) cathode showed good adhesion to the GDC/ScSZ electrolyte and low polarization resistance. The area specific resistance (ASR) of the BSCF (x = 0.2) cathode was 0.183 Ω cm² at 600 °C. The ASR of other BSCF (x = 0.4, 0.6, and 0.8) cathodes, however, was much higher than that of BSCF (x = 0.2).