A-site deficient Ba1−xCo0.7Fe0.2Ni0.1O3−δ cathode for intermediate temperature SOFC

A-site cation-deficient Ba_1−xCo_0.7Fe_0.2Nb_0.1O_3−δ (B_1−xCFN, x = 0.00-0.15) oxides are synthesized and evaluated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). The reactivity between B_1−xCFN and gadolinia doped ceria (GDC) is observed at different temperature, and no second phase is detected under 1050 °C. The increasing in A-site cation deficiency results in a steady decrease in cathode polarization resistance. Among the various B_1−xCFN oxides test, GDC based anode supported cells with B_0.9CFN cathode possess the smallest interfacial polarization resistance (R_p). The R_p is as low as 0.283 and 0.046 Ω cm² at 500 and 600 °C, respectively. The anode supported cell with B_0.9CFN provides maximum power densities of 1062 and 1139 mW cm⁻² at 600 and 650 °C, respectively. The results suggest that B_0.9CFN is a great potential cathode material for IT-SOFCs.     

In situ drop-coated BaZr0.1Ce0.7Y0.2O3−δ electrolyte-based proton-conductor solid oxide fuel cells with a novel layered PrBaCuFeO5+δ cathode

In order to develop a simple and cost-effective route to fabricate proton-conductor intermediate-temperature SOFCs, a dense BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) electrolyte was fabricated on a porous anode by in situ drop-coating. The PrBaCuFeO_5+δ (PBCF) composite oxide with layered perovskite structure was synthesized by auto ignition process and examined as a novel cathode for proton-conductor IT-SOFCs. The single cell, consisting of PBCF/BZCY/NiO-BZCY structure, was assembled and tested from 600 to 700 °C with humidified hydrogen (∼3% H₂O) as the fuel and the static air as the oxidant. An open-circuit potential of 1.01 V and a maximum power density of 445 mW cm⁻² at 700 °C were obtained for the single cell. A relatively low interfacial polarization resistance of 0.15 Ω cm² at 700 °C indicated that the PBCF is a promising cathode for proton-conductor IT-SOFCs.     

Fabrication and characterization of micro-tubular cathode-supported SOFC for intermediate temperature operation

We report the fabrication and characterization of a micro-tubular cathode-supported cell consisting of a Ce_0.9Gd_0.1O_1.95 electrolyte with a Ni–cermet anode on a porous La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ/Ce_0.9Gd_0.1O_1.95 (60:40 volume) tube (460 μm wall thickness and 2.26 mm diameter). The cells were fabricated by a cost-effective technique involving extrusion molding and slurry coating through a co-firing process. Densification of the ceria film (thickness < 15 μm) was successful by co-firing the laminated electrolyte with the porous cathode at 1200 °C. NiO–Ce_0.9Gd_0.1O_1.95 (Ni: Ce_0.9Gd_0.1O_1.95 = 50:50 in volume after reduction) was subsequently sintered on the electrolyte at 1100 °C to construct a 10 μm thick, porous and well-adherent anode. The cell having 1.5 cm tube length fed with humidified 30 vol.% H₂–Ar (3% H₂O) yielded the maximum power densities of 0.16, 0.13 and 0.11 W cm⁻², at 600, 550 and 500 °C, respectively. It was found that the cell performance is strongly dominated by the tube length, due to a high substrate resistance from the cathode current collections.     

High-performance PrBaCo2O5+δ-Ce0.8Sm0.2O1.9 composite cathodes for intermediate temperature solid oxide fuel cell

PrBaCo₂O_5+δ-Ce_0.8Sm_0.2O_1.9 (PBCO-SDC) composite material are prepared and characterized as cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). The powder X-ray diffraction result proves that there are no obvious reaction between the PBCO and SDC after calcination at 1100 °C for 3 h. AC impedance spectra based on SDC electrolyte measured at intermediate temperatures shows that the addition of SDC to PBCO improved remarkably the electrochemical performance of a PBCO cathode, and that a PBCO-30SDC cathode exhibits the best electrochemical performance in the PBCO-xSDC system. The total interfacial resistances R_p is the smallest when the content of SDC is 30 wt%, where the value is 0.035 Ω cm² at 750 °C, 0.072 Ω cm² at 700 °C, and 0.148 Ω cm² at 650 °C, much lower than the corresponding interfacial resistance for pure PBCO. The maximum power density of an anode-supported single cell with PBCO-30SDC cathode, Ni-SDC anode, and dense thin SDC/LSGM (La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ)/SDC tri-layer electrolyte are 364, 521 and 741 mW cm⁻² at 700, 750 and 800 °C, respectively.     

High-performance cathode-supported SOFCs prepared by a single-step co-firing process

Cathode-supported solid oxide fuel cells (SOFCs), comprising porous Pr_0.35Nd_0.35Sr_0.3MnO_3−δ (PNSM)/Sm_0.2Ce_0.8O_1.95 (SDC) cathode supports, SDC function layers, YSZ electrolyte membranes and NiO/SDC anode layers, were successfully fabricated via suspensions coating and single-step co-firing process. The microstructures of electrolyte membranes were observed with scanning electron microscope (SEM). The assembled single cell was electrochemically characterized with humidified hydrogen as fuel and ambient air as oxidant. The open circuit voltage (OCV) of the cell was 1.036 V at 650 °C, and the peak power densities were 657, 472, 290 and 166 mW cm⁻² at 800, 750, 700 and 650 °C, respectively. Impedance analysis indicated that the performance of cathode-supported cell was determined essentially by electrode polarization resistance, which suggested that optimizing electrodes was especially important for improving the cell performance.     

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.     

Prontonic ceramic membrane fuel cells with layered GdBaCo2O5+x cathode prepared by gel-casting and suspension spray

In order to develop a simple and cost-effective route to fabricate protonic ceramic membrane fuel cells (PCMFCs) with layered GdBaCo₂O_5+x (GBCO) cathode, a dense BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7) electrolyte was fabricated on a porous anode by gel-casting and suspension spray. The porous NiO–BaZr_0.1Ce_0.7Y_0.2O_3−δ (NiO–BZCY7) anode was directly prepared from metal oxide (NiO, BaCO₃, ZrO₂, CeO₂ and Y₂O₃) by a simple gel-casting process. A suspension of BaZr_0.1Ce_0.7Y_0.2O_3−δ powders synthesized by gel-casting was then employed to deposit BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7) thin layer by pressurized spray process on NiO–BZCY7 anode. The bi-layer with 10 μm dense BZCY7 electrolyte was obtained by co-sintering at 1400 °C for 5 h. With layered GBCO cathode synthesized by gel-casting on the bi-layer, single cells were assembled and tested with H₂ as fuel and the static air as oxidant. An open-circuit potential of 0.98 V, a maximum power density of 266 mW cm⁻², and a low polarization resistance of the electrodes of 0.16 Ω cm² was achieved at 700 °C.     

Co-doped Sr2FeNbO6 as cathode materials for intermediate-temperature solid oxide fuel cells

Sr₂Fe_1−xCo_xNbO₆ (0.1 ≤ x ≤ 0.9) (SFCN) oxides with perovskite structure have been developed as the cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). These materials are synthesized via solid-state reaction and characterized by XRD, SEM, electrical conductivity, AC impedance spectroscopy and DC polarization measurements. The reactivity tests show that the Sr₂Fe_1−xCo_xNbO₆ electrodes are chemically compatible with the Zr_0.85Y_0.15O_1.925 (YSZ) and Ce_1.9Gd_0.1O_1.95 (CGO) electrolytes at 1200 °C, and the electrode forms a good contact with the electrolyte after sintering at 1200 °C for 12 h. The total electrical conductivity that has a considerable effect on the electrode properties is determined in a temperature range from 200 °C to 800 °C. The highest conductivity of 5.7 S cm⁻¹ is found for Sr₂Fe_0.1Co_0.9NbO₆ at 800 °C in air. The electrochemical performances of these cathode materials are studied using impedance spectroscopy at various temperatures and oxygen partial pressures. Two different kinds of reaction rate-limiting steps exist on the Sr₂Fe_0.1Co_0.9NbO₆ electrode, depending on the temperature. The Sr₂Fe_0.1Co_0.9NbO₆ electrode on CGO electrolyte exhibits a polarization resistance of 0.74 Ω cm² at 750 °C in air, which indicates that the Sr₂Fe_0.1Co_0.9NbO₆ electrode is a promising cathode material for IT-SOFCs.     

Proton-conducting solid oxide fuel cells prepared by a single step co-firing process

Proton-conducting solid oxide fuel cells (SOFCs), consisting of BaCe_0.7In_0.3O_3−δ (BCI30)-NiO anode substrates, BCI30 anode functional layers, BCI30 electrolyte membranes and BCI30-LaSr₃Co_1.5Fe_1.5O_10−δ (LSCF) composite cathode layers, were successfully fabricated at 1150 °C, 1250 °C and 1350 °C respectively by a single step co-firing process. The fuel cells were tested with humidified hydrogen (∼3%H₂O) as the fuel and static air as the oxidant. The single cell co-fired at 1250 °C showed the highest cell performance. The impedance studies revealed that the co-firing temperature affected the interfacial polarization resistance of a single cell as well as its overall electrolyte resistance.     

Study on Sm1.8Ce0.2CuO4-Ce0.9Gd0.1O1.95 composite cathode materials for intermediate temperature solid oxide fuel cell

Sm_1.8Ce_0.2CuO₄-xCe_0.9Gd_0.1O_1.95 (SCC-xCGO, x = 0-12 vol.%) composite cathodes supported on Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte are studied for applications in IT-SOFCs. Results show that Sm_1.8Ce_0.2CuO₄ material is chemically compatible with Ce_0.9Gd_0.1O_1.95 at 1000 °C. The composite electrode exhibits optimum microstructure and forms good contact with the electrolyte after sintering at 1000 °C for 4 h. The polarization resistance (R_p) reduces to the minimum value of 0.17 Ω cm² at 750 °C in air for SCC-CGO06 composite cathode. The relationship between R_p and oxygen partial pressure indicates that the reaction rate-limiting step is the surface diffusion of the dissociative adsorbed oxygen on the composite cathode.     

Low-temperature protonic ceramic membrane fuel cells (PCMFCs) with SrCo0.9Sb0.1O3−δ cubic perovskite cathode

The SrCo_0.9Sb_0.1O_3−δ (SCS) composite oxide with cubic perovskite structure was synthesized by a modified Pechini method and examined as a novel cathode for protonic ceramic membrane fuel cells (PCMFCs). At 700 °C and under open-circuit condition, symmetrical SCS cathode on BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7) electrolyte showed low polarization resistances (R_p) of 0.22 Ωcm² in air. A laboratory-sized tri-layer cell of NiO–BZCY7/BZCY7/SCS was operated from 500 to 700 °C with humidified hydrogen (∼3% H₂O) as fuel and the static air as oxidant. A high open-circuit potential of 1.004 V, a maximum power density of 259 mW cm⁻², and a low polarization resistance of the electrodes of 0.14 Ωcm² was achieved at 700 °C.     

Effects of anode surface modification on the performance of low temperature SOFCs

An anode functional layer (AFL, ∼5 μm) for improving the cell performance was fabricated by the slurry spin coating method on the porous surface of an anode substrate. The effects of the AFL on the anode/electrolyte interfacial morphology and the Sm_0.2Ce_0.8O_1.9 (SDC) film deposition process were evaluated. And the electrochemical characteristics of the cells with and without the AFL were tested for comparison. With the AFL layer, the cell performance was greatly improved and the maximum power density was increased from 0.733 to 0.884 W cm⁻² at 600 °C and from 1.085 to 1.213 W cm⁻² at 650 °C. The systematical analysis indicated that the AFL could effectively reduce the anode polarization loss by increasing the three-phase boundary (TPB) length.     

A modified suspension spray combined with particle gradation method for preparation of protonic ceramic membrane fuel cells

In order to prepare a dense proton-conductive Ba(Zr_0.1Ce_0.7)Y_0.2O_3−δ (BZCY7) electrolyte membrane, a proper anode composition with 65% Ni₂O₃ in weight ratio was determined after investigating the effects of anode compositions on anode shrinkages for co-sintering. The thermal expansion margins between sintered anodes and electrolytes, which were less than 1% below 750 °C, also showed good thermal expansion compatibility. A suspension spray combined with particle gradation method had been introduced to prepare dense electrolyte membrane on porous anode support. After a heat treatment at 1400 °C for 5 h, a cell with La_0.5Sr_0.5CoO_3−δ (LSCO) cathode was assembled and tested with hydrogen and ammonia as fuels. The outputs reached as high as 330 mW cm⁻² in hydrogen and 300 mW cm⁻² in ammonia at 700 °C, respectively. Comparing with the interface of another cell prepared by dry-pressing method, this one also showed a good interface contact between electrodes and electrolyte. To sum up, this combined technique can be considered as commercial fabrication technology candidate.     

Evaluation of Ba0.5Sr0.5Co0.8Fe0.2O3−δ as a potential cathode for an anode-supported proton-conducting solid-oxide fuel cell

The potential application of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) as a cathode for a proton-conducting solid-oxide fuel cell based on BaCe_0.9Y_0.1O_2.95 (BCY) electrolyte was investigated. Cation diffusion from BCY to BSCF with the formation of a perovskite-type Ba²⁺-enriched BSCF and a Ba²⁺-deficient BCY at a firing temperature as low as 900 °C was observed, the higher the firing temperature the larger deviation of the A to B ratio from unit for the perovskites. Symmetric cell tests demonstrated the impurity phases did not induce a significant change of the cathodic polarization resistance, however, the ohmic resistance of the cell increased obviously. Anode-supported cells with the electrolyte thickness of ∼50 μm were successfully fabricated via a dual-dry pressing process for the single-cell test. Under optimized conditions, a maximum peak power density of ∼550 and 100 mW cm⁻² was achieved at 700 and 400 °C, respectively, for the cell with the BSCF cathode layer fired from 950 °C. At 500 °C, the ohmic resistance is still the main source of cell resistance. A further reduction in membrane thickness would envisage an increase in power density significantly.     

La2NiO4+δ potential cathode material on La0.9Sr0.1Ga0.8Mg0.2O2.85 electrolyte for intermediate temperature solid oxide fuel cell

La₂NiO_4+δ, a mixed ionic-electronic conducting oxide with K₂NiF₄ type structure, has been studied as cathode material with La_0.9Sr_0.1Ga_0.8Mg_0.2O_2.85 (LSGM) electrolyte for intermediate solid oxide fuel cells (IT-SOFCs). XRD results reveal excellent chemical compatibility between the La₂NiO_4+δ sample and LSGM electrolyte.A single cell (0.22 cm² active area) was fabricated with La₂NiO_4+δ as cathode, Ni-Sm_0.2Ce_0.8O_1.9 (2:1; w/w) as anode and LSGM as electrolyte. A thin buffer layer of Sm_0.2Ce_0.8O_1.9 (SDC) between anode and electrolyte was used to avoid possible interfacial reactions. The cell was tested under humidified H₂ and stationary air as fuel and oxidant, respectively. The electrochemical behaviour was evaluated by means of current-voltage curves and impedance spectroscopy. Microstructure and morphology of the cell components were analysed by SEM-EDX after testing.The maximum power densities were 160, 226, and 322 mW cm⁻² at 750, 800 and 850 °C, respectively with total polarisation resistances of 0.77, 0.48 and 0.31 Ω cm² at these temperatures. Cell performance remained stable when a current density of 448 mA cm⁻² was demanded for 144 h at 800 °C, causing no apparent degradation in the cell. The performance of this material may be further improved by reducing the electrolyte thickness and optimisation of the electrode microstructure.     

Initialization of a methane-fueled single-chamber solid-oxide fuel cell with NiO + SDC anode and BSCF + SDC cathode

The initialization of an anode-supported single-chamber solid-oxide fuel cell, with NiO + Sm_0.2Ce_0.8O_1.9 anode and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ + Sm_0.2Ce_0.8O_1.9 cathode, was investigated. The initialization process had significant impact on the observed performance of the fuel cell. The in situ reduction of the anode by a methane–air mixture failed. Although pure methane did reduce the nickel oxide, it also resulted in severe carbon coking over the anode and serious distortion of the fuel cell. In situ initialization by hydrogen led to simultaneous reduction of both the anode and cathode; however, the cell still delivered a maximum power density of ∼350 mW cm⁻², attributed to the re-formation of the BSCF phase under the methane–air atmosphere at high temperatures. The ex situ reduction method appeared to be the most promising. The activated fuel cell showed a peak power density of ∼570 mW cm⁻² at a furnace temperature of 600 °C, with the main polarization resistance contributed from the electrolyte.     

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.     

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.     

Polarization measurements on single-step co-fired solid oxide fuel cells (SOFCs)

Anode-supported planar solid oxide fuel cells (SOFC) were successfully fabricated by a single step co-firing process. The cells comprised of a Ni + yttria-stabilized zirconia (YSZ) anode, a YSZ or scandia-stabilized zirconia (ScSZ) electrolyte, a (La_0.85Ca_0.15)_0.97MnO₃ (LCM) + YSZ cathode active layer, and an LCM cathode current collector layer. The fabrication process involved tape casting of the anode, screen printing of the electrolyte and the cathode, and single step co-firing of the green-state cells in the temperature range of 1300–1330 °C for 2 h. Cells were tested in the temperature range of 700–800 °C with humidified hydrogen as fuel and air as oxidant. Cell test results and polarization modeling showed that the polarization losses were dominated by the ohmic loss associated with the electrodes and the activation polarization of the cathode, and that the ohmic loss due to the ionic resistance of the electrolyte and the activation polarization of the anode were relatively insignificant. Ohmic resistance associated with the electrode was lowered by improving the electrical contact between the electrode and the current collector. Activation polarization of the cathode was reduced by the improvement of the microstructure of the cathode active layer and lowering the cell sintering temperature. The cell performance was further improved by increasing the porosity in the anode. As a result, the maximum power density of 1.5 W cm⁻² was achieved at 800 °C with humidified hydrogen and air.     

Intermediate-temperature electrochemical performance of a polycrystalline PrBaCo2O5+δ cathode on samarium-doped ceria electrolyte

A-site cation-ordered PrBaCo₂O_5+δ (PrBC) double perovskite oxide was synthesized and evaluated as the cathode of an intermediate-temperature solid-oxide fuel cell (IT-SOFC) on a samarium-doped ceria (SDC) electrolyte. The phase reaction between PrBC and SDC was weak even at 1100 °C. The oxygen reduction mechanism was investigated by electrochemical impedance spectroscopy characterization. Over the intermediate-temperature range of 450–700 °C, the electrode polarization resistance was mainly contributed from oxygen-ion transfer through the electrode–electrolyte interface and electron charge transfer over the electrode surface. An area-specific resistance as low as ∼0.4 Ω cm² was measured at 600 °C in air, based on symmetric cell test. A thin-film SDC electrolyte fuel cell with PrBC cathode was fabricated which delivered attractive peak power densities of 620 and 165 mW cm⁻² at 600 and 450 °C, respectively.