Compaction pressure effect on microstructure and electrochemical performance of GdBaCo2O5+δ cathode for IT-SOFCs

In order to optimize the morphology of starting powder, raw GBCO powder synthesized via solid state reaction was repeatedly compacted by uniaxial die pressing at two apparent compaction pressures of 500 and 1000 MPa. The particle size distribution curves and SEM images indicated that, with increasing compaction pressure and number of compaction times, the larger particles in the powder were gradually broken apart and the particle size became small and uniform. Then the effect of pressing treatment for the starting GBCO particles on the microstructure and performance of sintered cathode was studied. The results demonstrated that, after being sintered under the same conditions, the cathode prepared from the treated GBCO particles showed a finer microstructure compared with that prepared from the raw GBCO particles. In addition, optimizing the morphology of the starting GBCO powder by pressing treatment could improved the cathode performance and made the polarization resistance of final cathode reduce from 1.33 Ω cm² to 0.40 Ω cm² at 600 °C.     

Effects of water atmosphere on chemical degradation of PrBa0.5Sr0.5Co1.5Fe0.5O5+δ electrodes

Protonic ceramic fuel cells (PCFC) based on a state-of-the-art electrolyte and cathode materials with extremely low ohmic resistance and high surface exchange rate in the intermediate temperature range (500–650 °C) have demonstrated exceptional power output in recent studies. However, reliable long-term operation remains a challenging issue in the development of PCFCs for practical applications. In particular, the water generated at the cathode has been reported to accelerate cation segregation and phase destruction of materials, thereby resulting in significant performance degradation. In this study, we investigate the underlying mechanism of the rapid chemical and electrochemical degradation of thin film PrBa_0.5Sr_0.5Co_1.5Fe_0.5O_5+δ model electrodes in a water atmosphere_. The electrochemical degradation, concurrent with the formation of Ba- and Sr-enriched surface clusters, was more significant in the water atmosphere than a dry atmosphere. Water adsorption onto the electrode surface was found to substantially alter the chemical states of the electrodes. In particular, the increased oxygen vacancies caused an increase in the electrostatic attraction, in turn, facilitating the cation segregation and phase destruction of the electrodes.     

A case study of mechanical properties of perovskite-structured Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen transport membrane

This study has investigated mechanical properties of perovskite-structured Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) oxygen transport membrane. The Young’s modulus and fracture toughness are determined by both macroscopic-scale and microscopic-scale methods. Both three-point and ring-on-ring bending tests as macroscopic-scale methods produce broadly similar results with a Young’s modulus, which is lower than that measured from micro-indentation method under a 10 N load. Young’s modulus and fracture toughness of BSCF show strongly dependent of the porosity. However, the fracture toughness of BSCF is independent of grain size. The fracture toughness determined by macroscopic-scale method is similar with that measured by microscopic-scale method. The crack shape of BSCF under a 10 N load is determined to be a median-radial mode. The intrinsic Young’s modulus and fracture toughness are determined to be 105.6 GPa and 1.49 MPa m^0.5, respectively, according the Minimum Solid Area (MSA) model. Annealing decreases the fracture toughness of BSCF between RT and 800 °C.     

Electrical properties of (La0.9Ca0.1)(Co1−xNix)O3−δ cathode materials for SOFCs

Modified perovskite ceramics (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ (x = 0–0.3) cathodes for solid oxide fuel cells (SOFCs) were synthesized by solid state reaction. The lattice parameters, electrical conductivity, activation energy, and microstructures of these specimens were investigated systematically in this study. The results exhibited that all specimens are rhombohedron structures and their tolerance factors were greater than 0.97, indicating that the perovskite was not distorted by Ni²⁺ cation substitution for the B site of (La_0.9Ca_0.1)CoO_3?δ. The microstructures of the (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ specimens showed good densification, and were well-sintered, with few pores. The electrical conductivity behavior conformed to the nature of a semiconductor, for all specimens. As x = 0.1, the electrical conductivity reached the maximum value of 750.3 S/cm at 800 °C, and the activation energy calculated from the Arrhenius plot of the electrical conductivity versus the reciprocal of temperature is 7.1 kJ/mol.The novelty of this study is its introduction of the concept of defect chemistry to explain the relationship between compensation mechanisms and electrical conductivity. The information gleaned regarding charge compensation mechanisms and defect formation may be valuable for a better understanding of the cathode of (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ ceramics used for SOFCs. Moreover, the information about oxygen content versus temperature is useful for expressing the relationship between electrical conductivity and composition. Therefore, we also used thermogravimetric analysis combined with the room-temperature oxygen content which was determined by iodometric titration to investigate the oxygen content from room temperature to high temperature, in air. Based on the experimental results, the (La_0.9Ca_0.1)(Co_0.9Ni_0.1)O_3?δ specimen shows high electrical conductivity. Consequently, it is identified as a promising candidate for cathode SOFC applications.     

Heterostructure interface effect on the ORR/OER kinetics of Ag–PrBa0.5Sr0.5Co2O5+δ for high-efficiency Li–O2 battery

Developing high-efficiency and cost-effective bifunctional electrocatalysts toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is an urgent issue for the oxygen-based electrochemical devices. Herein, an interface engineering concept has been proposed to achieve high-performance Ag–PBSC (Ag–PrBa_0.5Sr_0.5Co₂O_5+δ) heterostructure nanofibers catalyst. Benefiting from the significant ligand action and interparticle cooperation of exsolved Ag NPs and PBSC double perovskite, ORR/OER catalytic kinetics have been successfully boosted. In details, the PBSC double perovskite possessing abundant oxygen vacancies can provide oxygen channels and facilitate the transfer of electrons and oxygen. The embedded Ag NPs can deliver superior catalytic durability for the heterostructure interface. As expected, the as-synthesized Ag-PBSC heterostructure catalyst performs a favorable electrochemical performance in the oxygen-based applications. In alkaline media, the catalyst exhibits an excellent activity for ORR (E_onset: 0.88 V vs. RHE and E_1/2: 0.72 V vs. RHE) and OER (1.67 V at 10 mA cm^–2). When adopting the Ag–PBSC heterostructure catalyst in LOBs, the corresponding battery provides an outperforming capacity performance (13 000 mAh g^–1), low discharge–charge polarization (1.37 V), and considerable cycling performance (128 cycles at the restricted capacity of 3 000 mAh g^–1 and 400 mA g^–1). Apparently, the work described here confirms that the interface engineering of perovskites can open up opportunities to develop highly active and durable heterostructure electrocatalysts for multitudinous oxygen-based electrochemical applications.     

Evaluation of GdBaCuCo0.5Fe0.5O5+δ as cathode material for intermediate temperature solid oxide fuel cells

The GdBaCuCo_0.5Fe_0.5O_5+δ (GBCCF) layered perovskite oxide was evaluated as novel cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Its electrical conductivity was 9–13 S cm^?1 at 650–800 °C in air. The average thermal expansion coefficient (TEC) of GBCCF was 14.4 × 10^?6 K^?1, which was close to that of the typical electrolyte material. The cathode polarization resistance of GBCCF was 0.650 Ω cm² at 750 °C and it decreases to 0.118 Ω cm² when Ce_0.9Gd_0.1O_1.95 (GDC) was added to form a GBCCF–GDC composite cathode. Preliminary results indicated that layered perovskite GBCCF was a promising alternative cathode material for IT-SOFCs.     

Electrical characterization of co-precipitated LaBaCo2O5+δ and YBaCo2O5+δ oxides

REBaCo₂O_5+δ layered perovskite oxides (RE = Rare Earth) are promising cathodes for IT-SOFCs. In this work, a simple co-precipitation synthesis in aqueous medium was applied to prepare LaBaCo₂O_5+δ (LBC) and YBaCo₂O_5+δ (YBC) cathodes. The chemical and electrochemical properties of both materials were characterized via XRD, SEM, TPO, TG–DTA, 4-probe conductivity measurement, and EIS tests on symmetric cells. The coprecipitation synthesis revealed a promising preparation route: the measured ASR values of both materials were well comparable with the literature ones. A kinetic investigation of the O₂ reduction process was performed on LBC (600–800 °C, 5–100% O₂, v/v), whose results were analyzed with equivalent circuits. The main steps were identified (oxygen diffusion and charge transfer at high frequency, O₂ chemisorption at medium frequency), and their activation energy and reaction order were quantified. Aging tests (500 h time on stream, 500–800 °C) revealed quick deactivation for YBC and good stability for LBC.     

Variable optical properties of La0.5Sr0.5Co1-xNixO3-δ for high-temperature resistant code application

La_0.5Sr_0.5Co_1-xNi_xO_3-δ (x = 0, 0.1, 0.3, 0.5) ceramics were prepared via tape casting and solid state reaction process. The influence of Ni concentration on the optical properties of La_0.5Sr_0.5Co_1-xNi_xO_3-δ has been investigated. Results showed that the reflectance in the range of 0.3–15 μm decreased with the increment of Ni concentration, thereby causing a change in the color phase parameters and emissivity. Based on the difference in L* values and emissivity, the letters (HOT) and QR codes (NJTECH) were fabricated. The developed letters and QR codes could be identified both at room and high temperatures. Furthermore, the QR codes were read out successfully even underwent heat treatment at 1000 °C. The results in this work demonstrate a new application of La_0.5Sr_0.5Co_1-xNi_xO_3-δ ceramics.     

Conductivity and electrochemical performance of (Ba0.5Sr0.5)0.8La0.2CoO3−δ cathode for intermediate-temperature solid oxide fuel cell

This study reports the successful preparation of a single-phase cubic (Ba_0.5Sr_0.5)_0.8La_0.2CoO_3?δ perovskite by the citrate–EDTA complexing method. Its crystal structure, thermogravimetry, coefficient of thermal expansion, electric conductivity, and electrochemical performance were investigated to determine its suitability as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). Its coefficient of thermal expansion shows abnormal expansion at 300 °C, which is associated with the loss of lattice oxygen. The maximum conductivity of a (Ba_0.5Sr_0.5)_0.8La_0.2CoO_3?δ electrode is 689 S/cm at 300 °C. Above 300 °C, the electronic conductivity of (Ba_0.5Sr_0.5)_0.8La_0.2CoO_3?δ decreases due to the formation of oxygen vacancies. The charge-transfer resistance and gas phase diffusion resistance of a (Ba_0.5Sr_0.5)_0.8La_0.2CoO_3?δ–Ce_0.8Sm_0.2O_1.9 composite cathode are 0.045 Ω cm² and 0.28 Ω cm², respectively, at 750 °C.     

Tailoring the electrochemical reduction kinetics of dual-phase BaCe0.5Fe0.5O3-δ cathode via incorporating Mo for IT-SOFCs

The BaCe_0.5Fe_0.5O_3-δ (BCF) cathode consists of the ion-electron mixed conducting phase BaCe_0.15Fe_0.85O_3-δ (BCF1585) and the proton-conducting phase BaCe_0.85Fe_0.15O_3-δ (BCF8515). In this paper, the electrochemical performance is improved by incorporating the high valence element Mo into the BCF and applied to intermediate-temperature solid oxide fuel cells (IT-SOFCs). High-temperature X-ray diffraction (HT-XRD) and O₂-temperature programmed desorption (O₂-TPD) results show that Mo doping enhances the structural stability of BCF. The X-ray photoelectron spectroscopy (XPS) results suggest that the introduction of Mo increases the amount of adsorbed oxygen and thus the oxygen reduction reaction (ORR) catalytic activity. Compared to BCF, the polarization impedance of BaCe_0.5Fe_0.45Mo_0.05O_3-δ (BCFM) at 800 °C is 0.154 Ω·cm², a reduction of 22 %. Meanwhile, the BCFM output power at 800 °C is 778.01 mW·cm⁻², an improvement of 32.17 %, and maintains a stable current density after 250 h at 0.7 V. The results demonstrate that Mo doping is an effective strategy to enhance the electrochemical performance of BCF.     

Tuning Ba0.5Sr0.5Co0.8Fe0.2O3-δ cathode to high stability and activity via Ce-doping for ceramic fuel cells

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) fuel-cell cathode stands out because of its ultrahigh ionic conductivity and excellent electrocatalytic activity, but it is still very subject to instability. Here, a new strategy of Ce doping is proposed to boost the stability and activity of the BSCF cathode. A one-pot combustion method is employed to synthesize (Ba_0.5Sr_0.5)_1–xCe_xCo_0.8Fe_0.2O_3-δ (x=0–0.2) cathodes. Both BSCF and (Ba_0.5Sr_0.5)_0.9Ce_0.1Co_0.8Fe_0.2O_3-δ have a cubic perovskite structure. (Ba_0.5Sr_0.5)_0.8Ce_0.2Co_0.8Fe_0.2O_3-δ shows two phases of cubic perovskite and fluorite ceria. Proper Ce doping can boost the electrical conductivity of BSCF, and can dramatically reduce the polarization resistance of BSCF cathode. Ce doping significantly improved BSCF cathode long-term stability by 160 h. Moreover, ten-percent Ce doping in BSCF highly improves single-cell output performance from 516.33 mW cm^?2 to 629.75 mW cm^?2 at 750 °C. The results reveal that Ce doping as a potential strategy for enhancing the stability and activity of BSCF cathode is promising.     

Yttrium doping of Ba0.5Sr0.5Co0.8Fe0.2O3-δ part II: Influence on oxygen transport and phase stability

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) in its cubic perovskite phase has attracted much interest for potential use as oxygen transport membrane (OTM) due to its very high oxygen permeability at high temperatures. However, performance degradation due to a sluggish phase decomposition occurs when BSCF is operated below 840?°C. Partial B-site substitution of the transition metal cations in BSCF by larger and redox-stable cations has emerged as a potential strategy to improve the structural stability of cubic BSCF. In this study, the influence of yttrium doping (0…10?mol-%) on oxygen transport properties and stability of the cubic BSCF phase is assessed by in situ electrical conductivity relaxation (ECR) and electrical conductivity measurements during long-term thermal annealing both at 700?°C and 800?°C. Detailed phase analysis is performed by scanning electron microscopy (SEM) after long-term annealing of the samples in air at different temperatures.     

Investigation of oxygen ion transport and surface exchange properties of PrBaFe2O5+δ

The oxygen transport properties and chemical stability of PrBaFe₂O_5+δ (PBF) double-perovskite oxide were systematically investigated as a chemically stable, highly oxygen-permeable membrane and solid oxide fuel cell (SOFC) electrode under a CO₂-containing or reducing atmospheres. The oxygen permeation flux of 0.7 mm-thick samples and the oxygen ion conductivity were 4.7 × 10^?1 mL?cm^?2 min^?1 and 0.12 S?cm^?1 at 900 °C, respectively, which are comparable to those of PrBaCo₂O_5+δ, exhibiting the most superior performance among oxides with a double-perovskite structure. Moreover, the bulk diffusion and surface exchange coefficients estimated from the electrical conductivity relaxation analysis were generally comparable to those of PrBaCo₂O_5+δ. The characteristic thickness estimated from the membrane and conductivity relaxation tests was ～0.6 mm at 900 °C. The results indicate the significant influence of the surface exchange reaction on the permeability within a thickness of 0.5–1.7 mm. The PBF double-perovskite oxide exhibited superior chemical stability, compared to typical oxides such as PrBaCo₂O_5+δ under a CO₂-containing atmosphere. All results suggest that PrBaFe₂O_5+δ exhibits high oxygen diffusivity with high chemical stability under CO₂-containing or reducing atmospheres.     

Modeling of U-shaped Ba0.5Sr0.5Co0.8Fe0.2O3-δ hollow-fiber membrane for oxygen permeation

A mathematic model is developed for the perovskite-type mixed ionic-electronic conducting (MIEC) membrane,which makes it possible to simulate the process of oxygen separation in the U-shaped Ba0.5Sr0.5Co0.8Fe0.2O3-δ hollow-fiber membrane.The model correlates the oxygen permeation flux to the measurable variables.The trends of calculated results for purge operation coincide well with the experimental data,therefore the model is considerable for flux prediction under vacuum operation.Higher oxygen separation efficiency can be achieved with vacuum operation than purge operation.Parameter study with vacuum operation reveals that oxygen permeation flux increases with higher vacuum levels,and vacuum pressure of around 1.013 × 103 Pa is the optimal.Also,vacuum operation on the lumen side is much more efficient to achieve higher oxygen permeation flux compared with compression mode on the shell side.     

Evaluation of (Ba0.5Sr0.5)0.85Gd0.15Co0.8Fe0.2O3−δ cathode for intermediate temperature solid oxide fuel cell

A perovskite-type (Ba_0.5Sr_0.5)_0.85Gd_0.15Co_0.8Fe_0.2O_3?δ (BSGCF) oxide has been investigated as the cathode of intermediate temperature solid oxide fuel cells (IT-SOFCs). Coulometric titration, thermogravimetry analysis, thermal expansion and four-probe DC resistance measurements indicate that the introduction of Gd³⁺ ions into the A-site of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) leads to the increase in both oxygen nonstoichiometry at room temperature and electrical conductivity. For example, the conductivity of BSGCF is 148 S cm^?1 at 507 °C, over 4 times as large as that of BSCF. Furthermore, the electrochemical activity toward the oxygen reduction reaction is also enhanced by the Gd doping. Impedance spectra conducted on symmetrical half cells show that the interfacial polarization resistance of the BSGCF cathode is 0.171 Ω cm² at 600 °C, smaller than 0.297 Ω cm² of the BSCF cathode. A Ni/Sm_0.2Ce_0.8O_1.9 anode-supported single cell based on the BSGCF cathode exhibits a peak power density of 551 mW cm^?2 at 600 °C.     

Effect of Fe doping on the performance of suspension plasma-sprayed PrBa0.5Sr0.5Co2−xFexO5+δ cathodes for intermediate-temperature solid oxide fuel cells

PrBa_0.5Sr_0.5Co_2–xFe_xO_5+δ (PBSCF) (X = 0, 0.3, 0.4, and 0.5) is investigated as cathode material for intermediate-temperature solid oxide fuel cells. Suspension plasma spraying is used as a low cost and large-scale manufacturing process to prepare PBSCF cathodes. Fe substitution effects on the crystal structure and electrochemical performance are characterized. All plasma-sprayed PBSCF cathodes exhibit a pure and stable cubic structure. The suspension plasma-sprayed PBSCF deposits show a porous and fine structure, and the microstructures are insensitive to Fe substitution. Subsequent to Fe doping, the polarization resistance of PBSCF cathodes rapidly decreases for increasing Fe substitution concentration from 0 to 0.4. Further increase of the Fe doping concentration increases the cathode polarization instead. At 600 and 700 °C, a 20% Fe-doped (x = 0.4) PBSCF cathode exhibits remarkably low area-specific polarization resistances (R_p) of 0.074 Ω cm² and 0.012 Ω cm², respectively. Moreover, the R_p of all cathodes remains almost identical after isothermal annealing at 600 °C for 300 h. Furthermore, the thermally-sprayed porous metal-supported cell assembled with the optimal PBSCF cathode shows excellent performance with peak power densities of 0.37, 0.8, and 1.35 W cm⁻² at 500, 600, and 700 °C, respectively.     

Effect of microstructure on oxygen permeation of Ba0.5Sr0.5Co0.8Fe0.2O3−δ and SrCo0.8Fe0.2O3−δ membranes

The effect of grain size on oxygen permeation properties of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) and SrCo_0.8Fe_0.2O_3?δ (SCF) membranes was investigated by variation of the dwell time. The membrane microstructure was examined by field-emission scanning microscopy (FE-SEM) and then evaluated using a statistical approach. With longer dwell times the grain growth was stimulated and leaded to grains with a narrower size distribution. The grains of SCF (average size from 11.3 to 19.9 μm) were found to be smaller than those of BSCF (average size from 13.9 to 41.3 μm). The oxygen permeation flux of BSCF membranes was found to be independent of grain size in the range from 24 to 42 μm. However, membranes with smaller grains (13.9 μm) show a decreased oxygen permeation flux. For the SCF membranes a decrease in permeation flux with larger grains was observed for average grain sizes between 11.3 and 19.9 μm. By transmission electron microscopy (TEM) formation of an oxygen ordered SrCo_0.8Fe_0.2O_2.5 brownmillerite by-phase could be observed at the oxygen-depleted sweep side of the membrane.     

Surface kinetics and bulk transport in La2Ni0.5Cu0.5O4+δ membranes from conductivity relaxation

This work reports conductivity relaxation measurements on both uncoated (1.2 mm thick) and coated (2.0 mm thick) La₂Ni_0.5Cu_0.5O_4+δ membranes in the temperature range between 550 and 850 °C and oxygen partial pressures from 0.01 to 1.0 atm. The results show that surface kinetics has a significant effect on the relaxation profiles, especially at low temperatures and should not be neglected when extracting transport parameters. Oxygen chemical diffusion and surface exchange coefficients have been determined by transient conductivity with surface modification. Higher activation energy of surface exchange compared to bulk diffusion is observed for La₂Ni_0.5Cu_0.5O_4+δ, similar to that for La₂NiO_4+δ. Based on the oxygen partial pressure dependence of the surface exchange coefficient, it has been revealed that oxygen dissociative adsorption rate-limits the surface exchange.     

Synthesis,structure, optical and magnetic properties of Nd1−xAxMn0.5Co0.5O3−δ (A = Ba,Sr and Ca; x = 0 and 0.25)

The structural, optical, and magnetic properties of polycrystalline Nd_1-xA_xMn_0.5Co_0.5O_3−δ (A = Ba, Sr and Ca; x = 0 and 0.25) perovskite oxides were investigated. The powder XRD pattern demonstrates that the unit cell volume decreases with the changing A-site dopant type. The estimated bandgap energy (Eg) from UV–vis spectroscopic for NdMn_0.5Co_0.5O_3−δ, Nd_0.75Ba_0.25Mn_0.5Co_0.5O_3−δ, Nd_0.75Sr_0.25Mn_0.5Co_0.5O_3−δ and Nd_0.75Ca_0.25Mn_0.5Co_0.5O_3−δ are 3.27, 3.82, 3.79 and 3.53 eV respectively. The substitution of divalent element alters the absorption spectrum, while the redshift optical transition was observed with an increasing ionic radius of dopant. Temperature-dependent magnetization exposes that the Curie temperature (TC) gradually decreases with the decreasing size of alkaline earth metals, and glassy nature was observed at a lower applied magnetic field. The observation of TC can be well explained by the considering of the cationic size disorder parameter in A-site than the random distribution of B-site ions.