Enhanced performance of a single-chamber solid oxide fuel cell with an SDC-impregnated cathode

The electrochemical performance of anode-supported single-chamber solid oxide fuel cells (SC-SOFCs) with and without SDC-impregnated cathodes was compared in a diluted methane–oxygen mixture. These cells were made of conventional materials including yttrium-stabilized zirconia (YSZ) thin film, a Ni + YSZ anode and a La_0.7Sr_0.3MnO₃ (LSM) cathode. Our results showed that the cell performance was greatly enhanced with the SDC-impregnated LSM cathode. At a furnace temperature of 750 °C, the maximum power density was as high as 404 mW cm⁻² for a CH₄ to O₂ ratio of 2:1, which was 4.0 times higher than the cell with a pure LSM cathode (100 mW cm⁻²). The overall polarization resistance of the impregnated cell was 1.6 Ω cm², which was much smaller than that of the non-impregnated one (4.2 Ω cm²). The impregnation introduced SDC nanoparticles greatly extended the electrochemical active zone and hence greatly improved the cell performance.     

Performance and durability of nanostructured (La0.85Sr0.15)0.98MnO3/yttria-stabilized zirconia cathodes for intermediate-temperature solid oxide fuel cells

In this communication we report the fabrication of nanostructured (La_0.85Sr_0.15)_0.98MnO₃ (LSM)/yttria-stabilized zirconia (YSZ) composite cathodes consisting of homogeneously distributed and connected LSM and YSZ grains approximately 100 nm large. We also investigate for the first time the role of the cathode nanostructure on the performance and the durability of intermediate-temperature solid oxide fuel cells. The cathodes were fabricated using homogenous LSM/YSZ nanocomposite particles synthesized by co-precipitation, using YSZ nanoparticles of 3 nm as seed crystals. Detailed microstructural characterization by transmission electron microscopy with energy-dispersive X-ray spectroscopy revealed that many of the LSM/YSZ junctions in the cathode faced the homogeneously connected pore channels, indicating the formation of a considerable number of triple phase boundaries. The nanostructure served to reduce cathodic polarization. As a result, these anode-supported solid oxide fuel cells showed high power densities of 0.18, 0.40, 0.70 and 0.86 W cm⁻² at 650, 700, 750 and 800 °C, respectively, under the cell voltage of 0.7 V. Furthermore, no significant performance degradation of the cathode was observed during operation at 700 °C for 1000 h under a constant current density of 0.2 A cm⁻².     

La0.4Ce0.6O1.8–La0.8Sr0.2MnO3–8 mol% yttria-stabilized zirconia composite cathode for anode-supported solid oxide fuel cells

The composite cathodes of La_0.4Ce_0.6O_1.8 (LDC)–La_0.8Sr_0.2MnO₃ (LSM)–8 mol% yttria-stabilized zirconia (YSZ) with different LDC contents were investigated for anode-supported solid oxide fuel cells with thin film YSZ electrolyte. The oxygen temperature-programmed desorption profiles of the LDC–LSM–YSZ composites indicate that the addition of LDC increases surface oxygen vacancies. The cell performance was improved largely after the addition of LDC, and the best cell performance was achieved on the cells with the composite cathodes containing 10 wt% or 15 wt% LDC. The electrode polarization resistance was reduced significantly after the addition of LDC. At 800 °C and 650 °C, the polarization resistances of the cell with a 10 wt% LDC composite cathode are 70% and 40% of those of the cell with a LSM–YSZ composite cathode, respectively. The impedance spectra show that the processes associated with the dissociative adsorption of oxygen and diffusion of oxygen intermediates and/or oxygen ions on LSM surface and transfer of oxygen species at triple phase boundaries are accelerated after the addition of LDC.     

Ni/YSZ and Ni–CeO2/YSZ anodes prepared by impregnation for solid oxide fuel cells

In this paper, Ni/YSZ and Ni–CeO₂/YSZ anodes for a solid oxide fuel cell (SOFC) were prepared by tape casting and vacuum impregnation. By this method, the Ni content in the anode could be reduced compared to the traditional tape casting method. It was found that adding CeO₂ into the Ni/YSZ anode by a Ni(NO₃)₂ and Ce(NO₃)₃ mixed impregnation could further enhance cell performance. This was investigated in H₂ at 1073 K. XRD patterns indicated that CeO₂ and Ni were separate phases, and the CeO₂ addition could enhance the Ni dispersion on the YSZ framework surface which was observed by SEM images. It was shown that adding CeO₂ into the Ni anodes could decrease the cell polarization resistance. The maximum power density for cells with 25 wt.% Ni, 5 wt.% CeO₂–25 wt.% Ni/YSZ, or 10 wt.% CeO₂–25 wt.% Ni/YSZ anode was 230 mW cm⁻², 420 mW cm⁻² and 530 mW cm⁻², respectively, in H₂ at 1073 K. The OCV for these cells was 1.05–1.09 V, indicating that a dense electrolyte film was obtained by co-firing porous YSZ layer and dense YSZ layer.     

A comparative study of La0.8Sr0.2MnO3 and La0.8Sr0.2Sc0.1Mn0.9O3 as cathode materials of single-chamber SOFCs operating on a methane-air mixture

As candidates of cathode materials for single-chamber solid oxide fuel cells, La_0.8Sr_0.2MnO₃ (LSM) and La_0.8Sr_0.2Sc_0.1Mn_0.9O₃ (LSSM) were synthesized by a combined EDTA-citrate complexing sol-gel process. The solid precursors of LSM and LSSM were calcined at 1000 and 1150 °C, respectively, to obtain products with similar specific surface area. LSSM was found to have higher activity for methane oxidization than LSM due to LSSM's higher catalytic activity for oxygen reduction. Single cells with these two cathodes initialized by ex situ reduction had similar peak power densities of around 220 mW cm⁻² at 825 °C. The cell using the LSM cathode showed higher open-circuit-voltage (OCV) at corresponding temperatures due to its reduced activity for methane oxidation relative to LSSM. A negligible effect of methane and CO₂ on the cathode performance was observed for both LSM and LSSM via electrochemical impedance spectroscopy analysis. The high phase stability of LSSM under reducing atmosphere allows a more convenient in situ reduction for fuel cell initiation. The resultant cell with LSSM cathode delivered a peak power density of ∼200 mW cm⁻² at 825 °C, comparable to that from ex situ reduction.     

A new anode material for intermediate solid oxide fuel cells

A new anode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) with a composite of La_0.7Sr_0.3Cr_1−xNi_xO₃ (LSCN), CeO₂ and Ni has been synthesized. EDX analysis showed that 1.19 at% Ni was doped into the perovskite-type La_0.7Sr_0.3CrO₃ and Ce could not be detected in the perovskite phases. Results showed that the fine CeO₂ and Ni were highly dispersed on the La_0.7Sr_0.3Cr_1−xNi_xO₃ substrates after calcining at 1450 °C and reducing at 900 °C. The thermal expansion coefficient (TEC) of the as-prepared anode material is 11.8 × 10⁻⁶ K⁻¹ in the range of 30–800 °C. At 800 °C, the electrical conductivity of the as-prepared anode material calcined at 1450 °C for 5 h is 1.84 S cm⁻¹ in air and 5.03 S cm⁻¹ in an H₂ + 3% H₂O atmosphere. A single cell with yttria-stabilized zirconia (YSZ, 8 mol% Y₂O₃) electrolyte and the new materials as anodes and La_0.8Sr_0.2MnO₃ (LSM)/YSZ as cathodes was assembled and tested. At 800 °C, the peak power densities of the single cell was 135 mW cm⁻² in an H₂ + 3% H₂O atmosphere.     

Low-temperature solid oxide fuel cells with La1−xSrxMnO3 as the cathodes

La_1−xSr_xMnO₃ (LSM) has been widely developed as the cathode material for high-temperature solid oxide fuel cells (SOFCs) due to its chemical and mechanical compatibilities with the electrolyte materials. However, its application to low-temperature SOFCs is limited since its electrochemical activity decreases substantially when the temperature is reduced. In this work, low-temperature SOFCs based on LSM cathodes are developed by coating nanoscale samaria-doped ceria (SDC) onto the porous electrodes to significantly increase the electrode activity of both cathodes and anodes. A peak power density of 0.46 W cm⁻² and area specific interfacial polarization resistance of 0.36 Ω cm² are achieved at 600 °C for single cells consisting of Ni-SDC anodes, LSM cathodes, and SDC electrolytes. The cell performances are comparable with those obtained with cobalt-based cathodes such as Sm_0.5Sr_0.5CoO₃, and therefore encouraging in the development of low-temperature SOFCs with high reliability and durability.     

Evaluation of Sr0.88Y0.08TiO3–CeO2 as composite anode for solid oxide fuel cells running on CH4 fuel

Sr_0.88Y_0.08TiO₃ (YST) was synthesized and the performance of a YST–CeO₂ composite as an alternative anode for the direct utilization of CH₄ in solid oxide fuel cells (SOFCs) was investigated. X-ray diffraction showed that YST had good chemical compatibility with CeO₂ and YSZ (8 mol% Y-doped ZrO₂). The shrinkage of the YST–CeO₂ composite on sintering was less than that of pure YSZ and CeO₂, and its thermal-expansion behavior was similar to that of YSZ. With YSZ as electrolyte, ScSZ (10 mol% Sc-doped ZrO₂)–LSM (La_0.8Sr_0.2MnO₃) as cathode, and YST–CeO₂ composite as anode, single cells were prepared and tested in both H₂ and CH₄. The maximum power density obtained at 900 °C was 161.7 mW cm⁻² in H₂ atmosphere and 141.3 mW cm⁻² in CH₄. The results demonstrated the potential of using YST–CeO₂ composite as the anode for SOFCs.     

Effect of SDC-impregnated LSM cathodes on the performance of anode-supported YSZ films for SOFCs

Sm_0.2Ce_0.8O_1.9 (SDC)-impregnated La_0.7Sr_0.3MnO₃ (LSM) composite cathodes were fabricated on anode-supported yttria-stabilized zirconia (YSZ) thin films. Electrochemical performances of the solid oxide fuel cells (SOFCs) were investigated in the present study. Four single cells, i.e., Cell-1, Cell-2, Cell-3 and Cell-4 were obtained after the fabrication of four different cathodes, i.e., pure LSM and SDC/LSM composites in the weight ratios of 25/75, 36/64 and 42/58, respectively. Impedance spectra under open-circuit conditions showed that the cathode performance was gradually improved with the increasing SDC loading. Similarly, the maximum power densities (MPD) of the four cells were increased with the SDC amount below 700 °C. Whereas, the cell performance of Cell-4 was lower than that of Cell-3 at 800 °C, arising from the increased concentration polarization at high current densities. This was caused by the lowered porosity with the impregnation cycle. This disadvantage could be suppressed by lowering the operating temperature or by increasing the oxygen concentration at the cathode side. The ratio of electrode polarization loss in the total voltage drop versus current density showed that the cell performance was primarily determined by the electrode polarization. The contribution of the ohmic resistance was increased when the operating temperature was lowered. When a 100 ml min⁻¹ oxygen flow was introduced to the cathode side, Cell-3 produced MPDs of 1905, 1587 and 1179 mW cm⁻² at 800, 750 and 700 °C, respectively. The high cell outputs demonstrated the merits of the novel and effective SDC-impregnated LSM cathodes.     

Fabrication and characterization of a co-fired La0.6Sr0.4Co0.2Fe0.8O3−δ cathode-supported Ce0.9Gd0.1O1.95 thin-film for IT-SOFCs

A dense membrane of Ce_0.9Gd_0.1O_1.95 on a porous cathode based on a mixed conducting La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ was fabricated via a slurry coating/co-firing process. With the purpose of matching of shrinkage between the support cathode and the supported membrane, nano-Ce_0.9Gd_0.1O_1.95 powder with specific surface area of 30 m² g⁻¹ was synthesized by a newly devised coprecipitation to make the low-temperature sinterable electrolyte, whereas 39 m² g⁻¹ nano-Ce_0.9Gd_0.1O_1.95 prepared from citrate method was added to the cathode to favor the shrinkage for the La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ. Bi-layers consisting of <20 μm dense ceria film on 2 mm thick porous cathode were successfully fabricated at 1200 °C. This was followed by co-firing with NiO–Ce_0.9Gd_0.1O_1.95 at 1100 °C to form a thin, porous, and well-adherent anode. The laboratory-sized cathode-supported cell was shown to operate below 600 °C, and the maximum power density obtained was 35 mW cm⁻² at 550 °C, 60 mW cm⁻² at 600 °C.     

GdBaCo2O5+x layered perovskite as an intermediate temperature solid oxide fuel cell cathode

GdBaCo₂O_5+x (GBCO) was evaluated as a cathode for intermediate-temperature solid oxide fuel cells. A porous layer of GBCO was deposited on an anode-supported fuel cell consisting of a 15 μm thick electrolyte of yttria-stabilized zirconia (YSZ) prepared by dense screen-printing and a Ni–YSZ cermet as an anode (Ni–YSZ/YSZ/GBCO). Values of power density of 150 mW cm⁻² at 700 °C and ca. 250 mW cm⁻² at 800 °C are reported for this standard configuration using 5% of H₂ in nitrogen as fuel. An intermediate porous layer of YSZ was introduced between the electrolyte and the cathode improving the performance of the cell. Values for power density of 300 mW cm⁻² at 700 °C and ca. 500 mW cm⁻² at 800 °C in this configuration were achieved.     

Preparation of supported SrCeO3-based membrane by spin coating method

SrCe_0.9Y_0.1O_3−δ (SCY10) powder with a pure perovskite phase is prepared by solid-state reaction method. NiO is dispersed uniformly in SCY10 powder to fabricate NiO-SCY10 anode substrate. The starting powder, the mixture of SrCO₃, CeO₂ and Y₂O₃, is deposited directly on the green substrate instead of SCY10 powder by spin coating. After co-firing at 1300 °C for 3 h, the starting powder reacts to form SCY10 top layer on the substrate. SEM micrographs show that the top layer is defect-free and adheres well with the anode substrate without any delamination. A single fuel cell is assembled with anode-supported SCY10 membrane as electrolyte membrane and Ag as cathode. The electrochemical property of the fuel cell is tested with hydrogen as fuel in the temperature range of 600-800 °C. The open circuit voltage (OCV) reaches 1.05 V at 800 °C, and the maximum power density is 50 mW cm⁻², 155 mW cm⁻², 200 mW cm⁻² at 600 °C, 700 °C, 800 °C, respectively.     

Ba0.5Sr0.5Co0.8Fe0.2O3 − δ + LaCoO3 composite cathode for Sm0.2Ce0.8O1.9-electrolyte based intermediate-temperature solid-oxide fuel cells

A novel Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ + LaCoO₃ (BSCF + LC) composite oxide was investigated for the potential application as a cathode for intermediate-temperature solid-oxide fuel cells based on a Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte. The LC oxide was added to BSCF cathode in order to improve its electrical conductivity. X-ray diffraction examination demonstrated that the solid-state reaction between LC and BSCF phases occurred at temperatures above 950 °C and formed the final product with the composition: La_0.316Ba_0.342Sr_0.342Co_0.863Fe_0.137O_3 − δ at 1100 °C. The inter-diffusion between BSCF and LC was identified by the environmental scanning electron microscopy and energy dispersive X-ray examination. The electrical conductivity of the BSCF + LC composite oxide increased with increasing calcination temperature, and reached a maximum value of ∼300 S cm⁻¹ at a calcination temperature of 1050 °C, while the electrical conductivity of the pure BSCF was only ∼40 S cm⁻¹. The improved conductivity resulted in attractive cathode performance. An area-specific resistance as low as 0.21 Ω cm² was achieved at 600 °C for the BSCF (70 vol.%) + LC (30 vol.%) composite cathode calcined at 950 °C for 5 h. Peak power densities as high as ∼700 mW cm⁻² at 650 °C and ∼525 mW cm⁻² at 600 °C were reached for the thin-film fuel cells with the optimized cathode composition and calcination temperatures.     

Synthesis and properties of (La0.75Sr0.25)0.95MnO3±δ nano-powder prepared via Pechini route

(La_0.75Sr_0.25)_0.95MnO_3±δ (LSM) powders have been synthesized via a Pechini route. The prepared powders were characterized by XRD, SEM, XRF, BET and particle size distribution (PSD) analysis. It is shown that the morphology and structure of the oxide particles are significantly dependent on the preparation conditions such as the sort of surfactant and pH value of the starting solution. High purity, single phase, homogeneous, nanocrystalline LSM powders with slight aggregation were obtained using citric acid as complexing agent, ethylene glycol as surfactant and pH 1. The conductivity of the sintered LSM sample prepared from this nanocrystalline powders was mensurated about 200 S cm⁻¹ in air at 600–1000 °C. The impedance spectra of symmetric cells LSM–YSZ/YSZ/LSM–YSZ were measured in air and open circuit voltage condition. The optimal polarization resistance (R_p) of 0.175 Ω cm² at 750 °C and 0.07 Ω cm² at 800 °C was obtained in the sample with LSM to YSZ weight ratio of 49:51.     

Ni–YSZ-supported tubular solid oxide fuel cells with GDC interlayer between YSZ electrolyte and LSCF cathode

Highly sinterable gadolinia doped ceria (GDC) powders are prepared by carbonate coprecipitation and applied to the GDC interlayer in Ni–YSZ (yttria stabilized zirconia)-supported tubular solid oxide fuel cell in order to prevent the reaction between YSZ electrolyte and LSCF (La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ) cathode materials. The formation of highly resistive phase at the YSZ/LSCF interface was effectively blocked by the low-temperature densification of GDC interlayer using carbonate-derived active GDC powders and the suppression of Sr diffusion toward YSZ electrolyte via GDC interlayer by tuning the heat-treatment temperature for cathode fabrication. The power density of the cell with the configuration of Ni–YSZ/YSZ/GDC/LSCF–GDC/LSCF was as high as 906 mW cm⁻², which was 2.0 times higher than that (455 mW cm⁻²) of the cell with the configuration of Ni–YSZ/YSZ/LSM(La_0.8Sr_0.2MnO_3−δ)–YSZ/LSM at 750 °C.     

Improvement of the performances of tubular solid oxide fuel cells by optimizing co-sintering temperature of the NiO/YSZ anode-YSZ electrolyte double layers

The effects of co-sintering temperature on anode microstructure, electrolyte film microstructure, and final cell performance of tubular solid oxide fuel cells (SOFCs) were fully studied. The co-sintering of the NiO/YSZ anode-YSZ electrolyte double layers at temperature ranging from 1350 to 1400 °C for 5 h was carried out. Porosity and electrical conductivity were measured to examine the anodes microstructure, and the electrolyte films microstructure were characterized by scanning electronic microscope (SEM). A higher open current voltage (OCV) value of 0.99 V was achieved by co-sintering the cell at 1400 °C indicating denser electrolyte film, while the maximum power density of the cell co-sintered at 1380 °C was achieved with 322 mW cm⁻² at 800 °C, which was higher than that (241.3 mW cm⁻²) of the cell co-sintered at 1400 °C because of better anode microstructure.     

SmBaCo2O5+x double-perovskite structure cathode material for intermediate-temperature solid-oxide fuel cells

SmBaCo₂O_5+x (SBCO), an oxide with double-perovskite structure, has been developed as a novel cathode material for intermediate-temperature solid-oxide fuel cells (IT-SOFCs). The electrical conductivity of an SBCO sample reaches 815–434 S cm⁻¹ in the temperature range 500–800 °C. XRD results show that an SBCO cathode is chemically compatible with the intermediate-temperature electrolyte materials Sm_0.2Ce_0.8O_1.9 (SDC) and La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM). The polarization resistances of an SBCO cathode on SDC and LSGM electrolytes are 0.098 and 0.054 Ω cm² at 750 °C, respectively. The maximum power densities of a single cell with an SBCO cathode on SDC and LSGM electrolytes reach 641 and 777 mW cm⁻² at 800 °C, respectively. The results of this study demonstrate that the double-perovskite structure oxide SBCO is a very promising cathode material for use in IT-SOFCs.     

High temperature solid oxide electrolysis cell employing porous structured (La0.75Sr0.25)0.95MnO3 with enhanced oxygen electrode performance

An efficient steam electrolysis process for hydrogen production via a solid oxide electrolysis cell using porous network-like strontium doped lanthanum manganite (LSM)-yttria stabilized zirconia (YSZ) as the oxygen electrode material has been demonstrated. The porous network-like LSM powder was prepared by a nitrate–glycine combustion method. Impedance spectra and voltage-current density curves were measured as a function of cell current density and absolute humidity at 800 °C and 900 °C to characterize the cell performance. The cell area specific resistance (ASR) was 0.26 Ω cm² at 900 °C with 0.5 A/cm² current density and 50% absolute humidity (AH). The hydrogen production rate calculated from the Faraday's law was 362 ml/cm² h at 900 °C with 80 vol.% AH. The cell performance results indicate that the porous network-like LSM–YSZ is a promising oxygen electrode for high temperature electrolysis cells.     

Electrochemical performance of (Ba0.5Sr0.5)0.9Sm0.1Co0.8Fe0.2O3−δ as an intermediate temperature solid oxide fuel cell cathode

This study presents the electrochemical performance of (Ba_0.5Sr_0.5)_0.9Sm_0.1Co_0.8Fe_0.2O_3−δ (BSSCF) as a cathode material for intermediate temperature solid oxide fuel cells (IT-SOFC). AC-impedance analyses were carried on an electrolyte supported BSSCF/Sm_0.2Ce_0.8O_1.9 (SDC)/Ag half-cell and a Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF)/SDC/Ag half-cell. In contrast to the BSCF cathode half-cell, the total resistance of the BSSCF cathode half-cell was lower, e.g., at 550 °C; the values for the BSSCF and BSCF were 1.54 and 2.33 Ω cm², respectively. The cell performance measurements were conducted on a Ni-SDC anode supported single cell using a SDC thin film as electrolyte, and BSSCF layer as cathode. The maximum power densities were 681 mW cm⁻² at 600 °C and 820 mW cm⁻² at 650 °C.     

Electrochemical performance of La1.6Sr0.4NiO4-Ag composite cathodes for intermediate-temperature solid oxide fuel cells

La_1.6Sr_0.4NiO₄-Ag (LSN-Ag) composite cathodes are prepared and characterized by XRD and SEM, respectively. The electrochemical properties of the composite cathodes are investigated using AC impedance and DC polarization methods from 500 to 700 °C under different oxygen partial pressures. The polarization resistance (R_p) decreases with the increase of Ag content in the composite electrode. The addition of 5 vol.% Ag in LSN results in the lowest R_p of 0.21 Ω cm² at 700 °C in air. Oxygen partial pressure dependence study indicates that the charge transfer process is the reaction rate limiting step, while the diffusion process has no sensitive to the Ag loading. LSN-5Ag cathode exhibits the lowest overpotential of about 32 mV at a current density of 144 mA cm⁻² at 700 °C in air.