A novel Nb and Cu co-doped SrCoO3-δ cathode for intermediate temperature solid oxide fuel cells

The extensive explorations of potential cathode materials are prominently critical for the rapid development of high performance solid oxide fuel cells (SOFCs). Herein, we develop a novel Nb and Cu co-doped SrCoO_3-δ (SCNC) cathode base on solid state reaction, which exhibits decent compatibility with gadolinium doped cerium oxide (GDC) electrolyte. The SCNC is successfully stabilized with cubic structure at room temperature when incorporating of small amount of high valence Nb⁵⁺. Meanwhile, the oxygen vacancy concentration of SCNC is efficiently improved with the addition of Cu. The Nb and Cu co-doping also substantially promotes the electronic conductivity, achieving 550 S cm⁻¹ for the optical doped SrCo_0.85Nb_0.05Cu_0.10O_3-δ (SCNC10) at 400 °C. In addition, the polarization of SCNC is remarkably reduced, reaching as low as 0.021 Ω cm² for SCNC10 at 700 °C. The activation energy for reaction is also significantly lowered to 0.78 eV. The reaction order m is deduced to be about 0.30, implying that the rate determination step for SCNC10 is the charge transfer reaction. The peak power density of the single cell reaches 780 mW cm⁻² at 800 °C. All these outstanding performances demonstrate that SCNC is a promising cathode for SOFCs when operating at intermediate temperature (IT).     

Cobalt-free Sr0.7Y0.3CuO2+δ as a cathode for intermediate-temperature solid oxide fuel cell

Cobalt-free oxide Sr_0.7Y_0.3CuO_2+δ (SYCu) with one-dimensional structure has been investigated as potential cathode material for intermediate temperature solid oxide fuel cell (IT-SOFC) applications. The crystal structure, chemical compatibility, thermal expansion and electrochemical performance were examined by X-ray diffraction technique, electrochemical workstation and thermal dilatometer. One-dimensional structure Sr_1−xY_xCuO_2+δ and Sr_2−xY_xCuO_3+δ phases appeared as the main parts after calcination above 900 °C. The copper based oxide SYCu showed a thermal expansion coefficient (TEC) about 11.1 × 10⁻⁶/°C at 25–800 °C, exhibiting good physical compatibility with samarium doped cerium (SDC) electrolyte. High electro-catalytic performance was obtained for SYCu cathode in a symmetrical cell with a polarization resistance (R_p) of 0.029 Ω cm² and an overpotential of 4.9 mV at 100 mA/cm² at 800 °C, showing great promising use as cathode materials for IT-SOFCs. In addition, the polarization resistance of SYCu cathode remain constant after operation at 800 °C for 100 h, showing excellent long-term stability at operation temperature.     

Synthesis and characterization of aluminum-doped perovskites as cathode materials for intermediate temperature solid oxide fuel cells

(Ba_0.5Sr_0.5)(Fe_1-xAl_x)O_3-δ (BSFAx, x = 0–0.2) oxides have been synthesized as novel cobalt-free cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs) using a sol-gel method. The BSFAx (x = 0–0.2) materials have been characterized by X-ray diffraction and scanning electron microscopy. The electrical conductivities and electrochemical properties of the prepared samples have also been measured. At 800 °C, the conductivity drops from 15 S cm⁻¹ to 5 S cm⁻¹ when the doping level of aluminum is increased to 20%. The aluminum-doping concentration has important impacts on the electrochemical properties of BSFAx materials. The BSFA0.09 cathode shows a significantly lower polarization resistance (0.26 Ω cm²) and cathodic overpotential value (55 mV at the current density of 0.1 A cm⁻²) at 800 °C. Furthermore, an anode-supported single cell with BSFA0.09 cathode has been fabricated and operated at a temperature range from 650 to 800 °C with humidified hydrogen (∼3vol% H₂O) as the fuel and the static air as the oxidant. A maximum power density of 676 mWcm⁻² has been achieved at 800 °C for the single cell. We believe that BSFA0.09 is a promising cathode material for future IT-SOFCs application.     

Electrochemical performances of NdBa0.5Sr0.5Co2O5+x as potential cathode material for intermediate-temperature solid oxide fuel cells

Layered perovskite oxide NdBa_0.5Sr_0.5Co₂O_5+x is investigated as a cathode material for intermediate-temperature solid oxide fuel cells. The NBSC cathode is chemically compatible with the electrolyte La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) at temperatures below 1000 °C. It is metallic in nature and the maximum and minimum conductivities are 1368 S cm⁻¹ at 100 °C and 389 S cm⁻¹ at 850 °C. The area specific resistance (ASR) value for the NBSC cathode is as low as 0.023 Ω cm² at 850 °C. The electrolyte-supported fuel cell generates good performance with the maximum power density of 904, 774 and 556 mW cm⁻² at 850, 800 and 750 °C, respectively. Preliminary results indicate that NBSC is promising as a cathode for IT-SOFCs.     

Synthesis and electrochemical performance of La0.6Ca0.4Fe1−xNixO3 (x = 0.1, 0.2, 0.3) material for solid oxide fuel cell cathode

Polycrystalline samples of La_0.6Ca_0.4Fe_1−xNi_xO₃ (x = 0.1, 0.2, 0.3) (LCFN) are prepared by liquid mix method. The structure of the polycrystalline powders is analyzed with X-ray powder diffraction data. The XRD patterns are indexed as the orthoferrite similar to that of LaFeO₃ having a single phase with orthorhombic perovskite structure (Pnma). The morphological characterization is performed by scanning electron microscopy (SEM) obtaining a mean particle size less than 300 nm.Polarization resistance is studied using two different electrolytes: Y-stabilized zirconia (YSZ) and Sm-doped ceria (SDC). Electrochemical impedance spectroscopy (EIS) measurements of LCFN/YSZ/LCFN and LCFN/SDC/LCFN test cells are carried out. These electrochemical experiments are performed at equilibrium from 850 °C to room temperature, under both zero dc current intensity and air. The best value of area specific resistance (ASR) obtained is 0.88 Ω cm², corresponding to the La_0.6Ca_0.4Fe_0.9Ni_0.1O₃ material using SDC as electrolyte. The dc four-probe measurement indicates that La_0.6Ca_0.4Fe_0.9Ni_0.1O₃ exhibits fairly high electrical conductivity, over 300 S cm⁻¹ at T > 500 °C.     

Electrochemical performance of Pr1−xYxBaCo2O5+δ layered perovskites as cathode materials for intermediate-temperature solid oxide fuel cells

Pr_1−xY_xBaCo₂O_5+δ (x = 0.3, 0.5 and 0.7) oxides were prepared and evaluated as cathode materials for intermediate-temperature solid oxide fuel cells. The effect of Y-doping on the crystal structure, oxygen vacancy concentration, thermal expansion coefficient (TEC), electrical conductivity and cathode performance of Pr_1−xY_xBaCo₂O_5+δ was investigated. These properties were compared with that of GdBaCo₂O_5+δ having a middle element of lanthanides. Pr_1−xY_xBaCo₂O_5+δ shows TEC (∼17.6 × 10⁻⁶ K⁻¹) lower than that of undoped PrBaCo₂O_5+δ, but similar to the one for GdBaCo₂O_5+δ. Y-doping causes a decrease in electrical conductivity, but at the same time induces an increase in oxygen vacancy concentration. With increasing Y-doping level, the area specific resistance (ASR) of Pr_1−xY_xBaCo₂O_5+δ-based electrode in a symmetrical cell increases, and correspondingly, the peak power density of single-cell decreases slightly. Nevertheless, comparing to GdBaCo₂O_5+δ-based electrode, Pr_1−xY_xBaCo₂O_5+δ (x = 0.3–0.7) exhibits significantly lower ASR, and allows to obtain cells with higher maximum power density.     

Synthesis and characterization of Ba0.5Sr0.5Co0.8Fe0.1Ni0.1O3-δ cathode for intermediate-temperature solid oxide fuel cells

Perovskite Ba_0.5Sr_0.5Co_0.8Fe_0.1Ni_0.1O_3-δ (BSCFNi) oxide is synthesized and characterized as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The X-ray diffraction (XRD) spectra show that BSCFNi is chemical compatible with La_0.9Sr_0.1Ga_0.83Mg_0.17O_2.865(LSGM) electrolyte below 950 °C, but weak reaction is observed between BSCFNi cathode and Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte after calcined at 950 °C for 10 h. The XPS results indicate that transition metal cations in BSCFNi sample exist two different valence states, i.e., Co^4+/3+, Fe^4+/3+ and Ni^3+/2+. The average thermal expansion coefficient (TEC) of BSCFNi is 18.7 × 10^?6 K^?1 between 200 °C and 850 °C in air. The maximum electrical conductivity reaches 35.3 Scm^?1 at 425 °C in air. The polarization resistance of BSCFNi cathode on LSGM and SDC electrolytes are 0.033 and 0.066 Ωcm² at 800 °C, respectively. The maximum power density of LSGM electrolyte-supported single cell with BSCFNi cathode reaches 690 mWcm^?2 at 800 °C. These primarily results indicate that BSCFNi is a candidate cathode material for IT-SOFCs.     

Fabrication and evaluation of the electrochemical performance of the anode-supported solid oxide fuel cell with the composite cathode of La0.8Sr0.2MnO3−δ-Gadolinia-doped ceria oxide/La0.8Sr0.2MnO3−δ

The anode-supported single cell was constructed with porous Ni-Yittria-stabilized zirconia (YSZ) as the anode substrate, an airtight YSZ as the electrolyte, and a screen-printed La_0.8Sr_0.2MnO_3−δ (LSM)-Gadolinia-doped ceria (GDC)/LSM double-layer cathode. The SEM results show that the YSZ thin film is highly integrated, fully dense with a thickness of 13 μm, and exhibits excellent compatibility between cathode and electrolyte layers. The effects of feed rates of the reactants, temperature, and contact pressure between the current collector and the unit cell were systematically investigated. The results are based on the assumption that the anode contribution to the polarization resistance is negligible. Our analysis showed that the electrochemical reaction is limited by mass transfer control when the airflow rate is decreased to 500 ml min⁻¹. The maximum power density is 204.6 mW cm⁻² at 800 °C with H₂ and air at flow rates of 800 and 2000 ml min⁻¹, respectively. According to the AC-impedance data, the resistances of charge transfer at the electrode/electrolyte interface are 3.79 and 1.90 Ω cm². The resistances of oxygen-reduction processes are 3.63 and 1.01 Ω cm² at 700 and 800 °C, respectively. The results from the sensitivity analysis of the variation of contact pressure between current collectors and membrane electrode assembly (MEA) show that the influence is enhanced at the regions of the high current density.     

A high-performance Gd0.8Sr0.2CoO3–Ce0.9Gd0.1O1.95 composite cathode for intermediate temperature solid oxide fuel cell

Powders of Gd_0.8Sr_0.2CoO₃ (GSC) were prepared by a glycine–nitrate process. Symmetrical cathodes of GSC–50Ce_0.9Gd_0.1O_1.95 (GDC) (50:50 by volume) powders were deposited on GDC electrolyte pellets, and the electrochemical properties of the interfaces between the porous cathode and the electrolyte were investigated at intermediate temperature (500–750 °C) using electrochemical impedance spectroscopy. The addition of 50 vol.% GDC to GSC resulted in an additional factor ≈3 decrease in the area-specific resistance (ASR). The ASR values for the GSC–50GDC cathodes were as low as 0.064 Ω cm² at 700 °C and 0.16 Ω cm² at 600 °C, respectively. The maximum power density of a cell using the GSC–50GDC cathode was 356 mW cm⁻² at 700 °C.     

Preparation and electrochemical performance of Pr2Ni0.6Cu0.4O4 cathode materials for intermediate-temperature solid oxide fuel cells

Cathode material Pr₂Ni_0.6Cu_0.4O₄ (PNCO) for intermediate-temperature solid oxide fuel cells (IT-SOFCs) is synthesized by a glycine-nitrate process using Pr₆O₁₁, NiO, and CuO powders as raw materials. X-ray diffraction analysis reveals that nanosized Pr₂Ni_0.6Cu_0.4O₄ powders with K₂NiF₄-type structure can be obtained from calcining the precursors at 1000 °C for 3 h. Scanning electron microscopy shows that the sintered PNCO samples have porous microstructure with a porosity of more than 30% and grain size smaller than 2 μm. A maximum conductivity of 130 S cm⁻¹ is obtained from the PNCO samples sintered at 1050 °C. A single fuel cell based on the PNCO cathode with 30 μm Sm_0.2Ce_0.8O_1.9 (SCO) electrolyte film and a 1 mm NiO-SCO anode support is constructed. The ohmic resistance of the single Ni-SCO/SCO/PNCO cell is 0.08 Ω cm² and the area specific resistance (ASR) value is 0.19 Ω cm² at 800 °C. Cell performance was also tested using humidified hydrogen (3% H₂O) as fuel and air as oxidant. The single cell shows an open circuit voltage of 0.82 V and 0.75 V at 700 °C and 800 °C, respectively. Maximum power density is 238 mW cm⁻² and 308 mW cm⁻² at 700 °C and 800 °C, respectively. The preliminary tests have shown that Pr₂Ni_1−xCu_xO₄materials can be a good candidate for cathode materials of IT-SOFCs.     

Optimization on the electrochemical properties of La2NiO4+δ cathodes by tuning the cathode thickness

The electrochemical properties of La₂NiO_4+δ electrodes were investigated as a function of the electrode thickness based on three-electrode half cells. The electrocatalytic activity of the electrodes with the varied thicknesses ranging from 5 to 30 μm was surveyed by electrochemical impedance spectroscopy technique under open-current voltage conditions. The cathodic polarization curves of these electrodes were also inspected. The results indicated that the electrochemical properties of these electrodes were highly dependent on their thickness. The polarizations of involved electrode reaction processes displayed different variations with changing the electrode thickness. Tuning the electrode thickness was confirmed to be effective for optimizing the electrochemical properties. Among the investigated electrodes, the electrode with a thickness of ～20 μm achieved the optimal properties. At 800 °C in air, this electrode exhibited a polarization resistance of 0.24 Ω cm², an exchange current density of 201 mA cm^?2 and an overpotential of 40 mV at 200 mA cm^?2. On this ground, an anode-supported single cell with ～20 μm thick La₂NiO_4+δ cathode was fabricated. At 800 °C and using hydrogen fuel, this single cell attained a maximum powder density of 500 mW cm^?2.     

Effect of humidity on La0.4Sr0.6Co0.2Fe0.7Nb0.1O3−δ cathode of solid oxide fuel cells

Solid oxide fuel cells cathode often suffers from degradation caused by water vapor in air. Here, we report a cathode material, La_0.4Sr_0.6Co_0.2Fe_0.7Nb_0.1O_3−δ (LSCFN), and evaluate its humidity tolerance by the characterization of the materials in wet air with different water vapor concentration at different temperature. The X-ray diffraction analysis indicates that the crystal structure of LSCFN is relatively stable in wet air with no observable impurity. However, a crystalline contraction is observed. Exposure of wet air to LSCFN causes the decrease of electrical conductivity and increase of polarization resistance because H₂O might occupy the active sites for oxygen reduction reaction. For long-term operation, higher H₂O concentration in air accelerates the degradation of LSCFN cathode.     

Evaluation of layered perovskites YBa1−xSrxCo2O5+δ as cathodes for intermediate-temperature solid oxide fuel cells

This study is focused on the structural characteristics, oxygen nonstoichiometry, electrical conductivity, electrochemical performance and oxygen reduction mechanism of YBa_1−xSr_xCo₂O_5+δ (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.5). The high oxygen nonstoichiometry, δ = 0.18–0.43 at 700 °C, indicates the large oxygen vacancy concentrations in oxides. The electrical conductivity is improved due to the greater amount of electronic holes originated from the increased interstitial oxygen, and the conductivities of all samples are above 100 S cm⁻¹ at 400–700 °C in air. The results demonstrate the promising performance of YBa_1−xSr_xCo₂O_5+δ cathodes at intermediate temperatures, as evidenced by low area-specific resistances (ASRs) e.g. 0.21–0.59 Ω cm² at 700 °C. The lowest ASR, 0.44 Ω cm², and the cathodic overpotential, −40 mV at a current density of −136 mA cm⁻², are obtained in YBaCo₂O_5+δ cathode at 650 °C. The dependence of polarization resistance on oxygen partial pressure suggests that the charge transfer process is the rate-limiting step for oxygen reduction reaction in YBaCo₂O_5+δ cathode.     

Preparation and characterization of Nd2−xSrxCoO4+δ cathodes for intermediate-temperature solid oxide fuel cell

K₂NiF₄-type structural Nd_2−xSr_xCoO_4+δ (x = 0.8, 1.0, 1.2) was synthesized and evaluated as cathodes for intermediate-temperature solid oxide fuel cell (IT-SOFC). The crystal structure, thermal expansion, electrical conductivity and electrochemical properties were investigated by X-ray diffraction, dilatometry, DC four-probe method, AC impedance and polarization techniques. It is found that the electrochemical properties were remarkably improved with the increasing of Sr in the experiment range. Nd_0.8Sr_1.2CoO_4+δ showed the highest electrical conductivity of 212 S cm⁻¹ at 800 °C, the lowest polarization resistance and cathodic overpotential, 0.40 Ωcm² at 700 °C and 35.6 mV at a current density of 0.1 A cm⁻² at 700 °C, respectively. The chemical compatibility experiment revealed that Nd_0.8Sr_1.2CoO_4+δ cathode was chemically stable with the SDC electrolyte. The thermal expansion coefficient also increased with the Sr content.     

Novel perovskite-spinel composite conductive ceramics for SOFC cathode contact layer

Perovskite-spinel composite conductive ceramics are developed for solid oxide fuel cell (SOFC) cathode contact layer. The precursor of the composite materials includes micron-sized La_0.6Sr_0.4Co_0.2Fe_0.8O₃(LSCF) perovskite particles coated by the reduced nano-sized Mn_0.9Y_0.1Co₂O₄ (MYC) spinel material, and then it is sintered in-situ to obtain perovskite-spinel composites. The sintering activity of the composites is enhanced by using the reduced spinel powders. The conductive performance of the composite materials is effectively improved due to the high conductivity of perovskite LSCF particles utilized. Measured at 750^οC under constant current density of 400 mA/cm², after running 200 h, the area specific resistance (ASR) value of cathode contact layer remains relatively stable at around 5.4 mΩ cm². The developed LSCF-MYC composite as cathode contact layer presents good bonding strength with both cathode and interconnection, and shows obviously low contact resistance and high stability.     

Electrochemical performance of a Ni0.8Co0.15Al0.05LiO2 cathode for a low temperature solid oxide fuel cell

The electrochemical performance of the Ni_0.8Co_0.15Al_0.05LiO₂ (NCAL) cathode was investigated by comparing it with the traditional La_0.4Sr_0.6Co_0.2Fe_0.8O_3-δ (LSCF) and LSCF/Ce_0.9Gd_0.1O_2-δ (GDC) cathodes with a GDC electrolyte-supported solid oxide fuel cell (SOFC). It is found that the electrochemical performance of the cells with the NCAL and NCAL/GDC cathode is better than that of the cells with the LSCF and LSCF/GDC cathode at 550 °C. The results of the electrochemical performance tests of the cells with different NCAL/GDC mass ratios (10/0, 9/1, 8/2, 7/3 and 6/4) show that the NCAL/GDC composite cathode with the mass ratio of 8/2 has the best electrochemical performance. XRD results show that when the sintering temperature is higher than 700 °C, the NCAL/GDC composite will undergo chemical reactions and generate new phases, reducing the performance of the composite cathode. XPS results show that a small amount of Li₂CO₃ was formed on the surface of NCAL during cathode preparation, forming a special interface between NCAL, Li₂CO₃ and GDC. At the NCAL-Li₂CO₃/GDC interfaces, due to the migration and aggregation of Li⁺ to the interface, a space charge region may be formed in which the Li⁺ enrichment may lead to the formation of the region with a high oxygen vacancy concentration. A very high oxygen vacancy concentration at the NCAL-Li₂CO₃/GDC interfaces will provide sufficient oxygen ion conductivity for oxygen reduction reaction (ORR) and reduce the activation energy of the reaction. NCAL will be a potential cathode material that can reduce the operating temperature of the traditional SOFC to 550 °C or lower.     

Cathode reaction mechanism of porous-structured Sm0.5Sr0.5CoO3−δ and Sm0.5Sr0.5CoO3−δ/Sm0.2Ce0.8O1.9 for solid oxide fuel cells

The cathode reaction mechanism of porous Sm_0.5Sr_0.5CoO_3−δ, a mixed ionic and electronic conductor (MIEC), is studied through a comparison with the composite cathode Sm_0.5Sr_0.5CoO_3−δ/Sm_0.2Ce_0.8O_1.9. First, the cathodic behaviour of porous Sm_0.5Sr_0.5CoO_3−δ and Sm_0.5Sr_0.5CoO_3−δ/Sm_0.2Ce_0.8O_1.9 are observed for micro-structure and impedance spectra according to Sm_0.2Ce_0.8O_1.9 addition, thermal cycling and long-term properties. The cathode reaction mechanism is discussed in terms of frequency response, activation energy, reaction order and electrode resistance for different oxygen partial pressures p(O₂) at various temperatures. Three elementary steps are considered to be involved in the cathodic reaction: (i) oxygen ion transfer at the cathode-electrolyte interface; (ii) oxygen ion conduction in the bulk cathode; (iii) gas phase diffusion of oxygen. A reaction model based on the empirical equivalent circuit is introduced and analyzed using the impedance spectra. The electrode resistance at high frequency (R_c,HF) in the impedance spectra represents reaction steps (i), due to its fast reaction rate. The electrode resistance at high frequency is independent of p(O₂) at a constant temperature because the semicircle of R_c,HF in the complex plane of the impedance spectra is held constant for different values of p(O₂). Reaction steps (ii) and (iii) are the dominant processes for a MIEC cathode, according to the analysis results. The proposed cathode reaction model and results for a solid oxide fuel cell (SOFC) well describe a MIEC cathode with high ionic conductivity, and assist the understanding of the MIEC cathode reaction mechanism.